The direct electrochemical hydrogenation of unsaturated organic compounds containing C[double bond, length as m-dash]N and C[double bond, length as m-dash]O bonds using glassy carbon electrodes and a widely available Brønsted acid is demonstrated for a selection of α-ketoesters and benzoxazinones. In this simple set-up, the reduced products are formed with excellent selectivity, without the use of a redox mediator, and are easily recovered in good yields by extraction. The carbon-based electrode is essential to the observation of the hydrogenated product; no turnover is observed using platinum mesh.