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Dimerization of the xanthene dyes in the films, depending on their concentrations, and their photoinduced electron transfer processes to the titania gels were investigated using spectroscopic and photoelectric techniques. The dye having a higher dimerization constant in solution formed a higher amount of the dimer in the titania gel. There was only a slight difference between the photoelectric conversion efficiencies of the monomer and dimer. The titanium species were coordinated to the carboxylate of the dyes. The dimers as well as the monomers were encapsulated in the narrow spaces of the gel films and strongly interacted with the surrounding titania matrix in the dye-dispersing titania gel films. The dye having a more nucleophilic carboxylate oxygen could easily form the coordination complex with the titanium species. 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