A new method has been developed for the synthesis of disilylalkanes by Kolbe anodic oxidation of alpha-silylcarboxylic acids. Preparative electrolysis was carried out by constant current technique. The effect of various parameters (electricity consumption, current density, temperature, solvent, base and concentration of substrate) on the outcome of electrolytic process has been studied and evaluated. On the basis of optimal conditions found, the synthesis of three dimeric products Ph-2(Me)SiCH2CH2Si(Me)Ph-2, Ph(Me)(2)siCH(2)CH(2)Si(Me)(2)Ph and Me3SiCH2CH2SiMe3 was achieved in good yields by anodic decarboxylation of the corresponding acids Ph-2(Me)SiCH2CO2H, Ph(Me)(2)SiCH2CO2H and Me3SiCH2CO2H. (C) 2009 Elsevier Ltd. All rights reserved.