df = pd.merge(df1, df2, on=['User','Movie'], how='left', indicator='Exist')
df.drop('Rating', inplace=True, axis=1)
df['Exist'] = np.where(df.Exist == 'both', True, False)
print (df)
User Movie Exist
0 1 333 False
1 1 1193 True
2 1 3 False
3 2 433 False
4 3 54 True
5 3 343 False
6 3 76 True