Perovskite solar cells (PSCs) are developing rapidly and their power conversion efficiency (PCE) has been repeatedly refreshed, but their long-term stability still needs to be improved. At present, most of the preparation of high-efficiency PSCs is completed in the inert gas, with high cost and limited operating space, which is not conducive to its industrial application. Here, perovskite solar cells with mixed cation, displaying ultra-long stability, were successfully prepared in the air. Effects of A-site cation doping on the microstructure, optoelectronic properties and stability of the perovskite were systematically investigated. The experimental results show that FA⁺ and Cs⁺ co-doping improves the quality of perovskite films, modulates the energy level arrangement of perovskite/SnO₂, suppresses carrier complexation, and significantly improves the PCE, long-term, wet and thermal stability of the cell. The optimal PCE of Cs_0.05MA_0.35FA_0.6PbI₃ cells is 19.34%, maintaining 85% of the initial efficiency after reserving for 242 d in dark environment at (20±5) ℃ and <5% relative humidity. In contrast, the PCE of the MAPbI₃ cell decreased to 30% of the initial value after reserving for 112 d under the same test conditions. FA⁺ and Cs⁺ co-doping also significantly improved the thermal and moisture resistance of the cells. Cs_0.05MA_0.35FA_0.6PbI₃ PSCs remain 99% and 84% of initial PCE after aging for 96 h at (85±5) ℃ and 20%-30% relative humidity, (20±5) ℃ and 80%-90% relative humidity in the dark, respectively. In contrast, PCEs of MAPbI₃ PSCs under the same conditions remain only 70% and 56%. This study provides a reference for the preparation of highly efficient and ultra-long stable mixed cation solar cells in the air.