You create a new key/value pair on a dictionary by assigning a value to that key

d = {'key': 'value'}
print(d)  # {'key': 'value'}

d['mynewkey'] = 'mynewvalue'

print(d)  # {'key': 'value', 'mynewkey': 'mynewvalue'}

If the key doesn't exist, it's added and points to that value. If it exists, the current value it points to is overwritten.

To add multiple keys simultaneously, use dict.update():

>>> x = {1:2}
>>> print(x)
{1: 2}

>>> d = {3:4, 5:6, 7:8}
>>> x.update(d)
>>> print(x)
{1: 2, 3: 4, 5: 6, 7: 8}

For adding a single key, the accepted answer has less computational overhead.

dictionary[key] = value

Let's pretend you want to live in the immutable world and do not want to modify the original but want to create a new dict that is the result of adding a new key to the original.

In Python 3.5+ you can do:

params = {'a': 1, 'b': 2}
new_params = {**params, **{'c': 3}}

The Python 2 equivalent is:

params = {'a': 1, 'b': 2}
new_params = dict(params, **{'c': 3})

After either of these:

params is still equal to {'a': 1, 'b': 2}

and

new_params is equal to {'a': 1, 'b': 2, 'c': 3}

There will be times when you don't want to modify the original (you only want the result of adding to the original). I find this a refreshing alternative to the following:

params = {'a': 1, 'b': 2}
new_params = params.copy()
new_params['c'] = 3

or

params = {'a': 1, 'b': 2}
new_params = params.copy()
new_params.update({'c': 3})

Reference: What does `**` mean in the expression `dict(d1, **d2)`?

There is also the strangely named, oddly behaved, and yet still handy dict.setdefault().

This

value = my_dict.setdefault(key, default)

basically just does this:

try:
    value = my_dict[key]
except KeyError: # key not found
    value = my_dict[key] = default

E.g.,

>>> mydict = {'a':1, 'b':2, 'c':3}
>>> mydict.setdefault('d', 4)
4 # returns new value at mydict['d']
>>> print(mydict)
{'a':1, 'b':2, 'c':3, 'd':4} # a new key/value pair was indeed added
# but see what happens when trying it on an existing key...
>>> mydict.setdefault('a', 111)
1 # old value was returned
>>> print(mydict)
{'a':1, 'b':2, 'c':3, 'd':4} # existing key was ignored

This question has already been answered ad nauseam, but since my comment gained a lot of traction, here it is as an answer:

Adding new keys without updating the existing dict

If you are here trying to figure out how to add a key and return a new dictionary (without modifying the existing one), you can do this using the techniques below

python >= 3.5

new_dict = {**mydict, 'new_key': new_val}

python < 3.5

new_dict = dict(mydict, new_key=new_val)

Note that with this approach, your key will need to follow the rules of valid identifier names in python.

If you're not joining two dictionaries, but adding new key-value pairs to a dictionary, then using the subscript notation seems like the best way.

import timeit

timeit.timeit('dictionary = {"karga": 1, "darga": 2}; dictionary.update({"aaa": 123123, "asd": 233})')
>> 0.49582505226135254

timeit.timeit('dictionary = {"karga": 1, "darga": 2}; dictionary["aaa"] = 123123; dictionary["asd"] = 233;')
>> 0.20782899856567383

However, if you'd like to add, for example, thousands of new key-value pairs, you should consider using the update() method.

Here's another way that I didn't see here:

>>> foo = dict(a=1,b=2)
>>> foo
{'a': 1, 'b': 2}
>>> goo = dict(c=3,**foo)
>>> goo
{'c': 3, 'a': 1, 'b': 2}

You can use the dictionary constructor and implicit expansion to reconstruct a dictionary. Moreover, interestingly, this method can be used to control the positional order during dictionary construction (post Python 3.6). In fact, insertion order is guaranteed for Python 3.7 and above!

>>> foo = dict(a=1,b=2,c=3,d=4)
>>> new_dict = {k: v for k, v in list(foo.items())[:2]}
>>> new_dict
{'a': 1, 'b': 2}
>>> new_dict.update(newvalue=99)
>>> new_dict
{'a': 1, 'b': 2, 'newvalue': 99}
>>> new_dict.update({k: v for k, v in list(foo.items())[2:]})
>>> new_dict
{'a': 1, 'b': 2, 'newvalue': 99, 'c': 3, 'd': 4}
>>> 

The above is using dictionary comprehension.

First to check whether the key already exists:

a={1:2,3:4}
a.get(1)
2
a.get(5)
None

Then you can add the new key and value.

Add a dictionary (key,value) class.

class myDict(dict):

    def __init__(self):
        self = dict()

    def add(self, key, value):
        #self[key] = value # add new key and value overwriting any exiting same key
        if self.get(key)!=None:
            print('key', key, 'already used') # report if key already used
        self.setdefault(key, value) # if key exit do nothing


## example

myd = myDict()
name = "fred"

myd.add('apples',6)
print('\n', myd)
myd.add('bananas',3)
print('\n', myd)
myd.add('jack', 7)
print('\n', myd)
myd.add(name, myd)
print('\n', myd)
myd.add('apples', 23)
print('\n', myd)
myd.add(name, 2)
print(myd)

I think it would also be useful to point out Python's collections module that consists of many useful dictionary subclasses and wrappers that simplify the addition and modification of data types in a dictionary, specifically defaultdict:

dict subclass that calls a factory function to supply missing values

This is particularly useful if you are working with dictionaries that always consist of the same data types or structures, for example a dictionary of lists.

>>> from collections import defaultdict
>>> example = defaultdict(int)
>>> example['key'] += 1
>>> example['key']
defaultdict(<class 'int'>, {'key': 1})

If the key does not yet exist, defaultdict assigns the value given (in our case 10) as the initial value to the dictionary (often used inside loops). This operation therefore does two things: it adds a new key to a dictionary (as per question), and assigns the value if the key doesn't yet exist. With the standard dictionary, this would have raised an error as the += operation is trying to access a value that doesn't yet exist:

>>> example = dict()
>>> example['key'] += 1
Traceback (most recent call last):
  File "<stdin>", line 1, in <module>
KeyError: 'key'

Without the use of defaultdict, the amount of code to add a new element would be much greater and perhaps looks something like:

# This type of code would often be inside a loop
if 'key' not in example:
    example['key'] = 0  # add key and initial value to dict; could also be a list
example['key'] += 1  # this is implementing a counter

defaultdict can also be used with complex data types such as list and set:

>>> example = defaultdict(list)
>>> example['key'].append(1)
>>> example
defaultdict(<class 'list'>, {'key': [1]})

Adding an element automatically initialises the list.

Adding keys to dictionary without using add

        # Inserting/Updating single value
        # subscript notation method
        d['mynewkey'] = 'mynewvalue' # Updates if 'a' exists, else adds 'a'
        # OR
        d.update({'mynewkey': 'mynewvalue'})
        # OR
        d.update(dict('mynewkey'='mynewvalue'))
        # OR
        d.update('mynewkey'='mynewvalue')
        print(d)  # {'key': 'value', 'mynewkey': 'mynewvalue'}
        # To add/update multiple keys simultaneously, use d.update():
        x = {3:4, 5:6, 7:8}
        d.update(x)
        print(d) # {'key': 'value', 'mynewkey': 'mynewvalue', 3: 4, 5: 6, 7: 8}
        # update operator |= now works for dictionaries:
        d |= {'c':3,'d':4}
        # Assigning new key value pair using dictionary unpacking.
        data1 = {4:6, 9:10, 17:20}
        data2 = {20:30, 32:48, 90:100}
        data3 = { 38:"value", 99:"notvalid"}
        d = {**data1, **data2, **data3}
        # The merge operator | now works for dictionaries:
        data = data1 | {'c':3,'d':4}
        # Create a dictionary from two lists
        data = dict(zip(list_with_keys, list_with_values))