In [20]: df
Out[20]:
   A  B  C
0  1  2  1
1  2  3  0
2  3  4  0
3  4  5  1

# Note that df.C is a mask
# Note that this is np.where, not df.where. That is different.
In [21]: df['D'] = np.where(df.C, df.A, df.B)

In [22]: df
Out[22]:
   A  B  C  D
0  1  2  1  1
1  2  3  0  3
2  3  4  0  4
3  4  5  1  4