Electrochemical hydrogenation (ECH) is a particularly important and environmentally friendly approach to obtain biomass-based fuels and high value-added fine chemicals without using external hydrogen. Herein, we reported a highly efficient and selective ECH of furfural (FF) into furfuryl alcohol (FA) with Cu-based electrocatalyst in aqueous alkaline media. Under the optimal conditions, FA selectivity close to 100% with 99% FF conversion and total Faradaic efficiency above 95% were obtained with the electrocatalyst. Mechanism investigation suggests an ECH mechanism for FA formation, which is highly potential-dependent to FA selectivity, requiring low and well-matched concentrations between active hydrogen (Hads) species and FA radical on the Cu surface. Moreover, the electrocatalyst shows an excellent stability and recyclability during the eight-time consecutive recycling experiments, yielding a total amount of 1011 mg FA. This work thus highlights an important guidance for electrocatalytic upgrading of biomass-based platform molecules in an environmentally friendly way.