Methylammonium lead iodide (MAPI) has proven to be an exceptional light-absorber for single-junction thin-film solar cells. Nonetheless, degradation induced by environmental agents (air, moisture, heat) limits the stability of this hybrid perovskite. Here, we demonstrate that coating evaporated MAPI thin films with different hydrophobic molecules leads to a significant improvement in their stability. We especially investigated the degradation of MAPI and the subsequent formation of PbI2 at 150 °C by in situ XRD analysis and showed that this transformation is remarkably slowed down in films coated with trioctyl phosphine oxide and tridodecyl methylammonium iodide. This enhances the processability of such films, which is an important aspect for the fabrication of thin-film devices. Eventually, we demonstrate that such protected films can be implemented in single-junction n−i−p solar cells without any loss in the device efficiency.