You can use tuple unpacking in for statement:
for i, (key, value) in enumerate(a.iteritems()):
# Do something with i, key, value
>>> d = {'a': 'b'}
>>> for i, (key, value) in enumerate(d.iteritems()):
... print i, key, value
...
0 a b
Side Note:
In Python 3.x, use dict.items() which returns an iterable dictionary view.
>>> for i, (key, value) in enumerate(d.items()):
... print(i, key, value)