Chemically modified electrodes with supported titanium complexes have been generated for the first time by the reaction of TiCl4 with hydroxylated surfaces of glassy carbon or platinum electrodes. The resulting monolayers of titanium oxychloride species are not electroactive, but they can be evaluated with scanning Auger microprobe analysis and with a subsequent derivatization that uses (hydroxymethyl)ferrocene as a redox probe. The modified electrodes are stable under inert atmosphere but readily degrade upon exposure to air. Treatment of electrodes with other Ti complexes such as Ti(OEt)4, Cp2TiCl2, and CpTiCl3 gives either no reaction or electrochemically unstable surface moieties.