It's because python provides a special "tuple unpacking" syntax that many other languages don't have. I'll break apart what's going on:
The b, a
on the right of the equals is making a tuple (remember, a tuple is pretty much the same as a list, except you can't modify it). The a, b
on the left is a different syntax that's unpacking the tuple, i.e. it takes the first item in the tuple, and store it in the first variable listed, then it takes the second item and stored it in the second variable, and so forth.
This is what it looks like broken up in multiple steps:
a = 2
b = 3
my_tuple = a, b
print(my_tuple) # (2, 3)
b, a = my_tuple
print(a) # 3
print(b) # 2
And here's another, simpler examples of tuple unpacking, just to help wrap your mind around it:
x, y, z = (1, 2, 3)
print(x) # 1
print(y) # 2
print(z) # 3
By the way, Python's not the only one, Javascript can do it too, but with arrays:
[a, b] = [b, a];