Electrochemical and photochemical measurements demonstrated that dendritic phenylazomethines, which can make complexes with SnCl2 by a stepwise process, only permit an outbound electron transfer. The unique dendrimer effect allows efficient production of photo-generated radical ion pairs by suppressing their charge recombination. In sharp contrast, the phenylenevinylene or benzylether dendrimers, which lack a heteroatom or π-conjugation, did not exhibit such non-symmetric characters.