1In [9]: pd.Series(df.Letter.values,index=df.Position).to_dict()
2Out[9]: {1: 'a', 2: 'b', 3: 'c', 4: 'd', 5: 'e'}
3
1In [6]: df = pd.DataFrame(randint(0,10,10000).reshape(5000,2),columns=list('AB'))
2
3In [7]: %timeit dict(zip(df.A,df.B))
41000 loops, best of 3: 1.27 ms per loop
5
6In [8]: %timeit pd.Series(df.A.values,index=df.B).to_dict()
71000 loops, best of 3: 987 us per loop