Recovering chemical energy embedded in pollutants is significant in achieving carbon-neutral industrial wastewater treatment. Considering that industrial wastewater is usually treated in a decentralized manner, in situ utilization of chemical energy to achieve waste-to-treasure should be given priority. Herein, the chemical energy released by the electroreduction of Cr(VI) was used to enhance on-site H2O2 generation in a stacked flow-through electrochemical system. The driving force of water flow efficiently coupled O2 evolution with 2-e O2 reduction to facilitate H2O2 generation by transporting anode-produced O2 to the cathode. Meanwhile, the chemical energy released by Cr(VI) promoted O2 evolution and impeded H2 evolution by regulating the electrode potentials, accounting for the enhanced H2O2 generation. The system could completely reduce 10-100 ppm of Cr(VI), reaching the maximum H2O2 concentration of 2.41 mM. In particular, the H2O2 concentrations in the Cr(VI)-containing electrolyte were 10.6-88.1% higher than those in the Cr(VI) free electrolyte at 1.8-2.5 V. A 24-day continuous experiment demonstrated the high efficiency and stability of the system, achieving a 100% reduction efficiency for 100 ppm of Cr(VI) and producing ∼1.5 mM H2O2 at 1.8 V. This study presents a feasible strategy for Cr(VI) detoxification and synchronous on-site H2O2 generation, providing a new perspective for innovative Cr(VI) wastewater treatment toward resource utilization.