AbstractElectrocatalytic hydrogenation of 5‐hydroxymethylfurfural (HMF) is studied on solid metal electrodes in acidic solution (0.5 M H2SO4) by correlating voltammetry with on‐line HPLC product analysis. Three soluble products from HMF hydrogenation are distinguished: 2,5‐dihydroxymethylfuran (DHMF), 2,5‐dihydroxymethyltetrahydrofuran (DHMTHF), and 2,5‐dimethyl‐2,3‐dihydrofuran (DMDHF). Based on the dominant reaction products, the metal catalysts are divided into three groups: (1) metals mainly forming DHMF (Fe, Ni, Cu, and Pb), (2) metals forming DHMF and DMDHF depending on the applied potentials (Co, Ag, Au, Cd, Sb, and Bi), and (3) metals forming mainly DMDHF (Pd, Pt, Al, Zn, In, and Sb). Nickel and antimony are the most active catalysts for DHMF (0.95 mM cm−2 at ca. −0.35 VRHE and −20 mA cm−2) and DMDHF (0.7 mM cm−2 at −0.6 VRHE and −5 mA cm−2), respectively. The pH of the solution plays an important role in the hydrogenation of HMF: acidic condition lowers the activation energy for HMF hydro‐genation and hydrogenates the furan ring further to tetrahydrofuran.