Overcoming the issue of the stability of tin‐based perovskites is a major challenge for the commercial development of lead‐free perovskite solar cells. To attack this problem, a new organic cation, azetidinium (AZ), is incorporated into the crystal structure of formamidinium tin triiodide (FASnI3) to form the mixed‐cation perovskite AZxFA1‐xSnI3. As AZ has a similar size to FA but a larger dipole moment, hybrid AZxFA1‐xSnI3 films exhibit variation in optical and electronic properties on increasing the proportion of AZ. Trifluoromethylbenzene (CF3C6H5) serves as antisolvent to fabricate smooth and uniform perovskite films for the devices with an inverted planar heterojunction structure. The device performance is optimized to produce the greatest efficiency at x=0.15 (AZ15), for which a power conversion efficiency of 9.6 % is obtained when the unencapsulated AZ15 device is stored in air for 100 h. Moreover, the device retains 90 % of its initial efficiency for over 15 days. The significant performance and stability of this device reveal that the concept of mixed cations is a promising approach to stabilize tin‐based perovskite solar cells for future commercialization. Can we mix it? Yes we can! Mixing 15 % of azetidinium (AZ) inside a FASnI3 perovskite crystal enhances the device performance to attain a power conversion efficiency of 9.6 % with excellent stability for the unencapsulated device, which retains 90 % of its initial performance for over 15 days.