In recent years, air-processed MAPbI3 perovskite solar cells (PSCs) have attracted widespread interest from researchers worldwide because of their simple and low-cost fabrication process. Nonetheless, the ambient conditions usually bring about many adverse effects, such as imperfect crystallization and numerous defects in perovskite films, which seriously impact both the photoelectric performance and stability of the device. Therefore, in this work, a polymer dual-passivation strategy was employed by introducing ammonium polyphosphate (APP) as an additive to the green anti-solvent to accurately modify the perovskite layer. APP, which has abundant phosphate and ammonium groups, could simultaneously fill the I/Pb vacancies by Lewis acid-base reactions to restrain defect formation and improve the power conversion efficiency (PCE) of the ultimate device. On the other hand, the long molecular chains of the polymer with a certain flexural ability were easily congregated at the grain boundaries of the perovskite grains, thus enhancing the bending resistance. Consequently, high-quality perovskite films with a dense morphology and large grain size were obtained. Because of the reduced defect density and suppressed non-radiative recombination, the optimal PSC attained a champion PCE of 20.87% with negligible hysteresis. Furthermore, the non-encapsulated APP-modified flexible device also exhibited excellent bending resistance. Only 20% of its normalized PCE was lost after 150 bending cycles at room temperature. This simple, green, low-cost, and reliable strategy for preparing high-efficiency PSCs with good stability can facilitate its commercialization.