Catalytic hydrogenolyses of the benzylidene compounds, in which two oxygens, two nitrogens and both oxygen and nitrogen are bound to the α-carbon of the benzylidene, were investigated in order to know the condition of hydrogenolysis, which may affect one of the two bonds, if possible, and either one of the two when the two are different. Partial hydrogenolyses of the N, N'-benzylidenediamines and O, O'-benzylidenediethers and selective hydrogenolyses of the α-alkoxybenzylamines and N-(α-aminobenzyl) amides were realized by the method of using palladium-on-charcoal and Raney nickel catalyst. The catalytic hydrogenolyses of the latter two were influenced by solvent used and were selectively effected at the carbon-oxygen bond of the α-alkoxybenzylamines and at the carbon-amine nitrogen or carbon-amide nitrogen bond of the N-(α-aminobenzyl) amides.