A solution which adds a name to the new level and is easier on the eyes than other answers already presented:
df['newlevel'] = 'C'
df = df.set_index('newlevel', append=True).unstack('newlevel')
print(df)
# A B
# newlevel C C
# a 0 0
# b 1 1
# c 2 2
# d 3 3
# e 4 4