You are looking for size
:
In [11]: df.groupby(['col5', 'col2']).size()
Out[11]:
col5 col2
1 A 1
D 3
2 B 2
3 A 3
C 1
4 B 1
5 B 2
6 B 1
dtype: int64
To get the same answer as waitingkuo (the "second question"), but slightly cleaner, is to groupby the level:
In [12]: df.groupby(['col5', 'col2']).size().groupby(level=1).max()
Out[12]:
col2
A 3
B 2
C 1
D 3
dtype: int64