Electrolytic hydrogen production is heavily restricted by high-energy consumption majorly due to the relatively high potential of anodic oxygen evolution reaction (OER). Development of OER-alternative reaction at the anode has been recently proposed as a promising pathway to address the associated issues. In this work, we report a hybrid acid/alkali dual-electrolyte electrolyzer by coupling acidic hydrogen evolution reaction (HER) using commercial Pt/C cathode with alkaline Electrocatalytic glycerol oxidation (GOR) which is implemented by developing a nickel foam (NF) supporting Co3O4 nanosheets anode that shows low overpotential and high selectivity toward GOR for formate production. The hybrid acid/alkali electrolyzer only requires an applied voltage of 0.55 V to achieve the electrolytic current density of 10 mA·cm–2 for glycerol conversion into formate at the anode and H2 production at the cathode with the Faraday efficiency of about 100%. The present work may open a new avenue to maximize the electron utilization efficiency and implement the energy-saving green route for H2 generation.