Percentage Based Probability

I have this code snippet:

Random rand = new Random();
int chance = rand.Next(1, 101);

if (chance <= 25) // probability of 25%
{
    Console.WriteLine("You win");
}
else
{
    Console.WriteLine("You lose");
}

My question is, does it really calculate a 25% probability for winning here? Is the chance of winning for the player here is really 25%?

Edit:

I just wrote this:

        double total = 0;
        double prob = 0;
        Random rnd = new Random();
        for (int i = 0; i < 100; i++)
        {
            double chance = rnd.Next(1, 101);
            if (chance <= 25) prob++;
            total++;
        }
        Console.WriteLine(prob / total);
        Console.ReadKey();

And it's highly inaccurate. It goes from about 0.15 to 0.3.

But when I do more checks (change from (i < 100) to (i < 10000)) it's much more accurate.

Why is this? Why aren't 100 checks enough for it to be accurate?