The stability of perovskite solar cells is closely related to the defects in perovskite crystals, and a large number of crystal defects are caused by the solution method. In this study, resveratrol (RES), a green natural antioxidant abundant in knotweed and grape leaves, is introduced into perovskite films to passivate the defect. RES achieves defect passivation by interacting with uncoordinated Pb2+ in perovskite films. The defect formation energy of VPb and PbI on the surface of perovskite thin films is increased by RES doping, as calculated by density functional theory. The results show that the quality of the perovskite film is significantly improved, and the energy level structure of the device is optimized, and the power conversion efficiency (PCE) of the device is increased from 21.62% to 23.44%. RES can hinder the degradation of perovskite structures by O2− free radicals, and the device retained 88% of its initial PCE after over 1000 h in pure oxygen environment. The device retains 91% of the initial PCE after >1000 h at 25 °C and 50 ± 5% relative humidity. This work provides an idea for the use of natural and environmentally friendly additives to improve the efficiency and stability of devices.