Electrocatalytic small organic molecule oxidation coupled with hydrogen evolution reaction (HER) has attracted great attention recently for the coproduction of value‐added chemicals and hydrogen at ambient temperature. Herein, Pt/MnMoO 4 /NF has been developed as both anode and cathode for the concurrent high value‐added glycolic acid productions and high purity hydrogen generation. The prepared Pt/MnMoO 4 /NF nanosheet arrays exhibits high activity for selective ethylene glycol oxidation in polyethylene terephthalate hydrolysate solution, which shows a low potential of only 0.87 V to drive the current density of 100 mA cm −2 and the faradaic efficiency (glycolic acid) of ≈78.8% at the cell voltage of 1.0 V. Moreover, Pt/MnMoO 4 /NF nanosheet arrays also demonstrates excellent HER performance with ultralow overpotential as low as 31.02 mV to reach the current density of 10 mA cm −2 , which is much lower than most literature reports. This work may pave a new way for efficient coproduction of value‐added chemicals and hydrogen under ambient conditions powered by renewable electricity and the design of bifunctional catalysts.