A model acid, Ph-2(Me)SiCH2COOH, undergoes two competing anodic reaction.;, decarboxylation and desilylation under non-Kolbe conditions (e.g., at a C anode, in MeOH). The effects of anode material, current density, substrate concentration and base concentration on the two competing reactions have been investigated. The scope of the reaction was extended to other alpha-silyacetic acids of type R2R'SiCH2COOH, in order to study the influence by the substituents attached to silicon on the nature and distribution of products emerged from electrolysis. (C) 2012 Elsevier Ltd. All rights reserved.