Photosynthesis accounts for 90% of the energy conversion in the earth's ecosystem, which converts solar energy into chemical energy and produces organic matter efficiently. Inspired by photosynthesis, we constructed a biomimetic semiconductor material (VS4-biomass carbon) as a bifunctional electrode, where VS4 and biomass carbon simulated the photosystem and electron transfer chains in photosynthesis, effectively suppressing carrier recombination. Then VS4-biomass carbon is introduced into a photorechargeable battery (PRB) to achieve simultaneous photoelectric conversion and storage. Under illumination, the photogenerated electrons/holes through VS4-biomass carbon can boost the electrochemical kinetics of batteries and increase charge storage capacity. In addition, with the high light absorption capability and charge carrier separation ability of VS4-biomass carbon, the PRBs can be directly photocharged to 180 mAh g–1. Hence, this work provides a pathway for the efficient utilization of solar energy and high-performance energy storage devices.