There is a Combo.get method if needed, but you really shouldn't need it as the values dictionary provides the same data.
Here's how to get the index using the values variable.
import PySimpleGUI as sg
choices = ['aaa', 'bbb', 'ccc']
layout = [ [sg.Combo(choices, k='-COMBO-')],
[sg.Button('Go'), sg.Button('Exit')] ]
window = sg.Window('Window Title', layout)
while True:
event, values = window.read()
print(event, values)
if event == sg.WIN_CLOSED or event == 'Exit':
break
if event == 'Go':
if values['-COMBO-'] in choices:
idx = choices.index(values['-COMBO-'])
print(f'Index = {idx}')
else:
print('Selection not in choices')
window.close()

Here's the get method in use. You can also simply use values['-COMBO-']
It will return the current value. You can then use that to look up the "index" from the original choices.
import PySimpleGUI as sg
choices = ['aaa', 'bbb', 'ccc']
layout = [ [sg.Combo(choices, k='-COMBO-')],
[sg.Button('Go'), sg.Button('Exit')] ]
window = sg.Window('Window Title', layout)
while True:
event, values = window.read()
if event == sg.WIN_CLOSED or event == 'Exit':
break
if event == 'Go':
current = window['-COMBO-'].get()
if current in choices:
idx = choices.index(current)
print(f'Index = {idx}')
else:
print('Selection not in choices')
window.close()