Organic modification of sol-gel catalytic glassy electrodes made of a thin layer of organosilica doped with nitroxyl radical TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) crucially enhances stability in the waste-free oxidation of alcohols to carbonyls in water. Structural comparison between analogous films made of organosilica and unmodified SiO2 shows that the origin of the pronounced stable activity of the ORMOSIL film lies in high hydrophobic and also in the pronounced low degree of hydrophilicity.