AbstractThe sustainable production of chemicals and fuels from abundant solar energy and renewable carbon sources provides a promising route to reduce climate-changing CO₂ emissions and our dependence on fossil resources. Here, we demonstrate solar-powered formate production from readily available biomass wastes and CO₂ feedstocks via photoelectrochemistry. Non-precious NiOOH/α-Fe₂O₃ and Bi/GaN/Si wafer were used as photoanode and photocathode, respectively. Concurrent photoanodic biomass oxidation and photocathodic CO₂ reduction towards formate with high Faradaic efficiencies over 85% were achieved at both photoelectrodes. The integrated biomass-CO₂ photoelectrolysis system reduces the cell voltage by 32% due to the thermodynamically favorable biomass oxidation over conventional water oxidation. Moreover, we show solar-driven formate production with a record-high yield of 23.3 μmol cm⁻² h⁻¹ as well as high robustness using the hybrid photoelectrode system. The present work opens opportunities for sustainable chemical and fuel production using abundant and renewable resources on earth—sunlight, biomass and CO₂.