A thin poly(methyl methacrylate) (PMMA) film incorporating an amphiphilic ruthenium (Ru)-polypyridine complex having two (Ru2C16B) or four (Ru4C16B) aliphatic tails, and/or an amphiphilic viologen (LPV), was prepared on a water surface. Both interfacial and in-film photoinduced electron-transfer from the Ru-complex to LPV occurred more effectively in Ru2C16B as compared with Ru4C16B, suggesting more exposure of the hydrophilic head group of Ru2C16B at the him surface. Polarized optical second harmonic generation (SHG) studies on the Ru-complex-impregnated film also verified orientational difference between the two complexes; Ru4C16B tended to take more stand-up orientation as to the film surface. The SHG signal increased quadratically with the number of films in the presence of air gaps among them.