Methods are functions that are associated with a class. Methods are only created when you retrieve them from an already defined class; a method is a wrapper around a function, with a reference to the class as well (and optionally a reference to the instance).
What happens in the first case is: Python compiles your class definition Adder. It finds the decorator definition and a function. The decorator is passed the function, returning a new function. That function is added to the class definition (stored in the class __dict__). All this time you are dealing with a python function, not a method. That happens later.
When you then call a(1), a lookup reveals that the instance doesn't have a __call__ but the Adder class does, so it is retrieved using __getattribute__(). This finds a function (your deco decorator), which is a descriptor so it's __get__() method is called (so Adder.__call__.__get__(a, Adder)), returning a bound method, which is then called and passed in the 1 value. The method is bound because instance is not None when __get__() is called. Your decorator, which wrapped a function at class building time, prints False because it was passed an unwrapped function to start with.
In the second case, however, you retrieve a method (again via __getattribute__() calling __get__() on the undecorated Adder2.__call__ function), this time unbound (as there is no instance, only a class passed to __get__() (the full call is Adder2.__call__.__get__(None, Adder2)), and you then decorate that method. Now ismethod() prints True.
Note that in Python 3, the latter case changes. In Python 3 there no longer is a concept of an unbound method, only functions and bound methods. The term 'bound' is thus dropped altogether. Your second case would also print False as Adder2.__call__.__get__(None, Adder2) returns a function in that case.