In Python 3.6 the fastest way is still the WouterOvermeire one. Kikohs' proposal is slower than the other two options.
import timeit
setup = '''
import pandas as pd
import numpy as np
df = pd.DataFrame(np.random.randint(32, 120, 100000).reshape(50000,2),columns=list('AB'))
df['A'] = df['A'].apply(chr)
'''
timeit.Timer('dict(zip(df.A,df.B))', setup=setup).repeat(7,500)
timeit.Timer('pd.Series(df.A.values,index=df.B).to_dict()', setup=setup).repeat(7,500)
timeit.Timer('df.set_index("A").to_dict()["B"]', setup=setup).repeat(7,500)
Results:
1.1214002349999777 s # WouterOvermeire
1.1922008498571748 s # Jeff
1.7034366211428602 s # Kikohs