A general procedure is described for the attachment to antimony-doped tin dioxide (SnO2:Sb), tin-doped indium oxide (In2O3:Sn), or glass surfaces of molecules with known electron transfer or excited state properties, e.g. [Ru-(bpy)2(4,4’-(CO2H)2bpy)](PF6)2 (bpy = 2,2’-bipyridine, 4,4’-(CO2H)2bpy = 4,4’-dicarboxy-2,2’-bipyridine), based on the interaction between surface hydroxyls and carboxylic acid groups. Integrations of cyclic voltammetric waveforms on the metal oxide electrode give maximum surface coverages of GAMMA approximately 1 x 10(-10) mol/cm2 for the ruthenium complex, which corresponds to a monolayer coverage. Atomic force microscope (AFM) measurements reveal that the metal oxide surfaces are highly roughened with root mean square roughnesses in the range 4-6.5 nm for tin oxide. The smaller organics, N-methyl-N-viologenpropanoic acid bis(hexafluorophosphate), [MV-CO2H](PF6)2, and 10H-phenothiazine-10-propanoic acid, PTZ-CO2H, display similar surface coverages. Resonance Raman measurements on surfaces containing the ruthenium complex imply that attachment to SnO2, In2O3, and TiO2 is via an ester bond. For SiO2, two modes of binding are suggested, a majority by a chelating carboxylato link and a minority by ester formation. Binding constants for surface attachment were measured in CH2Cl2 at 298 K by equilibration, which gave K = 8 x 10(4) M-1 on both SnO2:Sb and In2O3:Sn. Surface molecular assemblies have been prepared containing [Ru(bpy)2(4,4’-(CO2H)2bpy)](PF6)2 and [Os(bpy)2(4,4’-(CO2H)2 bpy)](PF6)2, [MV-CO2H(PF6)2, and PTZ-CO2H. In these assemblies, separate waves are observed for the different redox couples at potentials near those found for surfaces containing only a single component. Emission decay of the metal-to-ligand charge transfer (MLCT) excited state of [Ru(bpy)2(4,4’-(CO2H)2bpy)](PF6)2 attached to the glass backings of metal oxide electrodes or to glass slides was found to be nonexponential with average lifetimes ([tau]) from < 5 to 600 ns with CH2Cl2 in the external solution. [tau] increases as surface coverage decreases. There is evidence for excited state-ground state interactions by a red-shift in the emission maximum as surface coverage increases. Emission decay remains nonexponential even on surfaces that are lightly covered. Emission is nearly completely quenched on the semiconductor surfaces, with [tau] < 5 ns. The bound Ru(II) emitters on glass were quenched by electron or energy transfer to the coattached quenchers [MV-CO2H](PF6)2, PTZ-CO2H, or [Os(bpy)2(4,4’-(CO2H)2-bpy)](PF6)2, suggesting that lateral electron and energy transfer can occur across the surface. Surface lifetime quenching also occurred in the presence of added 10-methyl-10-phenothiazene in the external CH2Cl2 solution. The kinetics of lifetime quenching did not follow Stern-Volmer kinetics but could be fit to a model in which there are both quenchable and unquenchable sites on the same surface.