Electrochemical reduction via paired electrolysis has been used to achieve deoxygenative reduction of ketones. As a result of the complexing of ketones with the triphenylphosphine radical cation generated by anodic oxidation, the reduction of carbonyl groups occurs readily. Through spontaneous β-scission of phosphoranyl radicals, C-O bonds are cleaved to form benzylic radical intermediates. These radical species are either able to abstract hydrogen from MeCN or undergo reduction at the cathode to give carbanions, upon workup forming reductive hydrogenation of ketones.