AbstractTin halide perovskites are an appealing alternative to lead perovskites. However, owing to the lower redox potential of Sn(II)/Sn(IV), particularly under the presence of oxygen and water, the accumulation of Sn(IV) at the surface layer will negatively impact the device's performance and stability. To this end, this work has introduced a novel multifunctional molecule, 1,4‐phenyldimethylammonium dibromide diamine (phDMADBr), to form a protective layer on the surface of Sn‐based perovskite films. Strong interactions between phDMADBr and the perovskite surface improve electron transfer, passivating uncoordinated Sn(II), and fortify against water and oxygen. In situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) analysis confirms the enhanced thermal stability of the quasi‐2D phase, and hence the overall enhanced stability of the perovskite. Long‐term stability in devices is achieved, retaining over 90% of the original efficiency for more than 200 hours in a 10% RH moisture N₂ environment. These findings propose a new approach to enhance the operational stability of Sn‐based perovskite devices, offering a strategy in advancing lead‐free optoelectronic applications.