Anodic oxidation of Ru(OH2)(6)(2+) at potentials where the oxidation proceeds beyond Ru(OH2)(6)(3+) leads to the deposition of adherent coatings on the electrode surface. The deposit, believed to be a ruthenium oxide-hydroxide, exhibits pronounced electrocatalytic activity toward the oxidation of alcohols. Electrocatalytically active material was also prepared within Nafion(R) coatings on electrodes by anodic oxidation of RU(OH2)(6)(2+) incorporated into the coatings. The product of the oxidation in Nafion(R) appears to be Ru-4(OH)(12)(4+). Procedures for formation of catalyst coatings and their characterization by both spectroscopic and electrochemical measurements are presented.