Electrochemical glycerol oxidation reaction (GOR) is an attractive alternative anodic reaction to oxygen evolution reaction for a variety of electrolytic synthesis, thanks to the possibility of mass production of glycerol from biomass and the relative low thermodynamic potential of GOR. The development of high-activity cheap electrocatalysts toward GOR yet faces a daunting challenge. Herein, we experimentally prepare a new range of high entropy alloy (HEA) self-supported electrodes with uniform HEA nanoparticles grown on carbon cloth. The systematic electrochemical studies verify that the HEA-CoNiCuMnMo electrode exhibits attractive performance for GOR electrocatalysis with low overpotential and high selectivity toward formate products. The surface atomic configurations of HEA-CoNiCuMn-Mo are studied by a self-developed machine learning-based Monte Carlo simulation, which points out the catalytic active center to be Mo sites coordinated by Mn, Mo, and Ni. We further develop a hybrid alkali/acid flow electrolytic cell by pairing alkaline GOR with acidic hydrogen evolution reaction using the HEA-CoNiCuMnMo and the commercial RhIr/Ti as the anode and the cathode, respectively, which only requires an applied voltage of 0.55 V to reach an electrolytic current density of 10 mA cm −2 and maintains long-term electrolysis stability over 12 days continuous running at 50 mA cm −2 with Faraday efficiencies of over 99% for H 2 in the cathode and 92% for formate production in the anode.

WS2 nanosheets hold great promise for a variety of applications yet faces a grand challenge in terms of large‐scale synthesis. We report a reliable, scalable, and high‐yield (>93 %) synthetic strategy to fabricate WS2 nanosheets, which exhibit highly desirable electrocatalytic properties toward both the alkaline sulfion (S2−) oxidation reaction (SOR) and the acidic hydrogen evolution reaction (HER). The findings prompted us to develop a hybrid alkali‐acid electrochemical cell with the WS2 nanosheets as bifunctional electrode catalysts of alkaline anodic SOR and acidic cathodic HER. The proof‐of‐concept device holds promise for self‐power or low‐electricity electrolytic H2 generation and environmentally friendly recycling of sulfion with enhanced electron utilization efficiency.