Silica gel coating films doped with Ru(bpy)32+ complexes were prepared by the sol−gel method from a hydrolyzed tetraethoxysilane solution containing [Ru(bpy)32+]Cl2·6H2O. UV−visible optical absorption spectra, fluorescence emission spectra, fluorescence efficiency and lifetime, and infrared absorption spectra were measured for the films dried at various temperatures. The fluorescence band attributed to the transition from the metal-to-ligand charge transfer excited state to the ground state of Ru(bpy)32+ was found to show blue shift on sol-to-gel film conversion, red shift with increasing drying temperature up to 200 °C, and then blue shift again over 200 °C. The fluorescence lifetime increased and the fluorescence efficiency decreased with increasing drying temperature. In the as-deposited film, the complexes are thought to be surrounded by the solvent molecules which interact with the silanol groups of the gel network so strongly that the Franck−Condon excited state of the complex may be relaxed to a le...