By using np.sort
with duplicated
df[pd.DataFrame(np.sort(df[['Name1','Name2']].values,1)).duplicated()]
Out[614]:
Name1 Name2 Value
1 Ale Juan 1
Performance
df=pd.concat([df]*100000)
%timeit df[pd.DataFrame(np.sort(df[['Name1','Name2']].values,1)).duplicated()]
10 loops, best of 3: 69.3 ms per loop
%timeit df[~df[['Name1', 'Name2']].apply(frozenset, axis=1).duplicated()]
1 loop, best of 3: 3.72 s per loop