The first is used to initialise newly created object, and receives arguments used to do that:
class Foo:
def __init__(self, a, b, c):
# ...
x = Foo(1, 2, 3) # __init__
The second implements function call operator.
class Foo:
def __call__(self, a, b, c):
# ...
x = Foo()
x(1, 2, 3) # __call__