The pronounced efficiency disparity between ambient-air-fabricated organic solar cells (OSCs) and nitrogen-glovebox-processed devices poses a major obstacle to industrial-scale manufacturing. The instability of the organic electron transport layer (ETL) materials in air undoubtedly affects the carrier transport properties, which significantly reduces the power conversion efficiency (PCE) of the devices. Here, based on the antioxidant strategy, the stability of PDINN in air is enhanced by doping PDINN with the antioxidant C60-OH, thereby successfully achieving the all-air preparation of OSCs. Eventually, the PCE of the air-prepared green OSCs based on PM6:BTP-eC9 and PM6:PTQ10:BTP-eC9 (o-xylene) achieves 19.35% and 20.22%, respectively, after being optimized by the antioxidant strategy. Moreover, C60-OH remarkably improves the operational stability of the device in air with a T80 lifetime of over 1060 h, which is higher than that of undoped device (416 h). Furthermore, the PCE of large-area (25 cm2) modules based on PDINN:C60-OH attains 16.47%. This study highlights the potential of the antioxidant strategy to fabricate high-efficiency and stable organic photovoltaics in air, significantly promoting the development of OSCs.