Silica films doped with water soluble porphyrin, 5,10,15,20-tetrakis[4-(N-trimethyl)ammonio]phenylporphyrin (TTMAPP), were deposited on the surface of a glass slide at 25–35°C by the liquid phase deposition (LPD) method from saturated hydrofluorosilicic acid or fluorosilicate solutions containing TTMAPP. It was doped as protonated (cationic) or neutral forms depending on the deposition condition. Two forms are reversibly converted by heat treatment or environments. The lifetime of excited triplet state of TTMAPP in silica films was more than ten times longer than that in aqueous solutions used for deposition. Fairly strong molecular interaction of excited triplet states in aqueous solutions was almost eliminated in silica films. The LPD method is useful to fix firmly organic dyes in silica at high concentrations without undesirable molecular interactions.