Aqueous colloidal silica suspensions modified by incorporation of tris(2,2’-bipyridyl)ruthenium(II) and zinc(II) tetrakis(N-methyl-4-pyridyl)porphyrin into the particle matrix were prepared. The photophysical properties of the complexes in this environment were investigated using laser flash photolysis and steady-state luminescence techniques. The excited states exhibit nonexponential kinetics and their lifetimes are increased compared to homogeneous aqueous solutions. The metal-to-ligand charge transfer state of the Ru(II) complex is not affected by the presence of dissolved oxygen, whereas a fraction of the triplet states of the porphyrin is quenched by O-2. Didodecyldimethylammonium ion was used to build surfactant bilayers supported on the silica surface. The possibility of using this system for transmembrane electron transfer is discussed.