Long‐chain organic halide salts are widely used in perovskite‐based optoelectronic devices for surface passivation owing to their capability to interact with the surface defects of perovskites. Here, aluminum oxide (AlOx) is introduced via atomic layer deposition onto octylammonium iodide (OAI) to exploit the benefits of organic halide salts without generating undesired defects. The devices incorporating AlOx on OAI‐treated perovskite (OAI/AlOx) show enhancement in both device performance and photo‐stability compared to those with only treatment. A diffusion of aluminum from AlOx into the perovskite through surface characterization contributes to a uniform photo‐generated carrier transport in both the surface and the bulk of the perovskite absorber. In addition, it is revealed that light‐induced two‐dimensional perovskite formation on OAI/AlOx. This may be ascribed to preventing the loss of OA cations due to the presence of AlOx, leading to a decrease in the number of iodine anions which suppresses the light‐induced degradation of corresponding devices. Consequently, the devices show over 24% efficiency and retain their efficiency over 1000 hours under continuous light illumination.