Introducing solar energy directly into flexible energy storage systems is an environmentally friendly, efficient, and low-cost strategy. Herein, we constructed a photoelectrode based on flexible carbon cloth (CC) to promote the oxygen evolution reaction (OER) and effectively reduce the charging voltage of flexible zinc-air batteries (ZABs), inspired by the photosynthesis process in leaves. The implementation of sulfur vacancies (VS) and oxygen doping in nanoscale molybdenum disulfide (MoS2) effectively enhances the separation efficiency of photo-generated electron-hole pairs, and adjusts its band structure to improve the oxidation capability. The constructed photocathode with defect-rich MoS2 (D-MoS2) exhibits a low overpotential of 235 mV at 10 mA cm−2 for OER. The sandwich flexible ZABs based on D-MoS2 achieve a low charge voltage around 1.3 V and an ultra-high energy efficiency greater than 90 % under illumination at 0.1 mA cm−2. This strategy provides a new insight for the application of light energy in smart wearable energy storage devices.