Electrochemistry of organosilicon compounds and intermediate species containing Si-O and Si=O bonds is considered. Dichloro-,  dialkoxy- and dithiosilanes react with electrogenerated superoxide anion to give transient silanones which have been trapped by their insertion into Si-O and Si-H bonds of siloxanes and triorganosilanes; the process thus results in functional siloxane products. The analogous reaction with monochlorosilanes leads to bis-silylperoxides. Peroxodicarbonate anion prepared by cathodic activation of O₂ in the presence of CO₂ reacts with hydrosilanes yielding, with monohydrosilanes, the derivatives of silylcarboxylic acids whereas with dihydrosilanes corresponding cyclosiloxanes were formed. The mechanisms and kinetics of the considered processes are discussed.