The electrocatalytic hydrogenolysis (ECH) of lignin model compounds has been investigated under galvanostatic control at Raney nickel electrodes in aqueous ethanol. The influence of current density, concentration of substrate and temperature on the efficiency of the carbon-oxygen bond hydrogenolysis was studied with benzyl phenyl ether and the optimum conditions leading to its total conversion were found. The effect, on the current efficiency, of replacing the phenyl group by an alkyl group (e.g. benzyl methyl ether) and of substituting hydrogens on aromatic rings by methoxy groups was investigated using the optimum electrolysis conditions. The electrocatalytic hydrogenolysis of beta-phenoxyethylbenzene and alpha -phenoxyacetophenone, representatives of two other kinds of carbon-oxygen linkage in lignin, was also carried out.