Abstract Recent years have witnessed considerable progress in the development of solar cells based on lead halide perovskite materials. However, their intrinsic instability remains a limitation. In this context, the interplay between the thermal degradation and the hydrophobicity of perovskite materials is investigated. To this end, the salt 1‐(4‐ethenylbenzyl)‐3‐(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctylimidazolium iodide (ETI), is employed as an additive in hybrid perovskites, endowing the photoactive materials with high thermal stability and hydrophobicity. The ETI additive inhibits methylammonium (MA) permeation in methylammonium lead triiodide (MAPbI 3 ) occurring due to intrinsic thermal degradation, by inhibiting out‐diffusion of the MA + cation, preserving the pristine material and preventing decomposition. With this simple approach, high efficiency solar cells based on the unstable MAPbI 3 perovskite are markedly stabilized under maximum power point tracking, leading to greater than twice the preserved efficiency after 700 h of continuous light illumination and heating (60 °C). These results suggest a strategy to tackle the intrinsic thermal decomposition of MAI, an essential component in all state‐of‐the‐art perovskite compositions.

Retarding Thermal Degradation in Hybrid Perovskites by Ionic Liquid Additives