This line of code works by creating a tuple, and then destructuring it to assign two variables at once. The result is that both a and b on the left-hand-side are assigned the results of expressions on the right-hand-side which are calculated using the original values of a and b.
The expression on the right-hand-side is b, a + b which is equivalent to (b, a + b), i.e. it creates a tuple with two components.
The assignment target on the left-hand-side is a, b which is equivalent to (a, b), i.e. it assigns to two variables simultaneously, using the values of the two components from the tuple respectively. This is called a destructuring assignment.
This is convenient because if the two assignments were written separately, as in the code below, then it would not have the desired effect. The first line changes a's value, and then the new value would (incorrectly) be used to calculate b:
# WRONG!
a = b
b = a + b