4-[ N-ethyl- N-(2-hydroxyethyl)]amino-4 ′-nitro-azobenzene (DR1)-doped phenyl group substituted silica films were prepared by a sol–gel method. The films were optically poled by the coherent superposition of 1064 and 532 nm beams from a Q-switched Nd:YAG laser. To discuss the effects of the modifier group, interaction between DR1 molecules and the matrix was investigated. The delocalization of π electrons occurred between DR1 molecules and the phenyl-silica hybrid matrix, and that consequently the polarized DR1 molecules could be stabilized. By use of the optimized optical poling technique, optical storage was successfully demonstrated for a phenyl-silica hybrid film doped with DR1.