Abstract: | Two‐dimensional lead and tin halide perovskites were prepared by intercalating the long alkyl group 1‐hexadecylammonium (HDA) between the inorganic layers. We observed visible‐light absorption, narrow‐band photoluminescence, and nanosecond photoexcited lifetimes in these perovskites. Owing to their hydrophobicity and stability even in humid air, we applied these perovskites in the decarboxylation and dehydrogenation of indoline‐2‐carboxylic acids. (HDA)2PbI4 or (HDA)2SnI4 were investigated as photoredox catalysts for these reactions, and quantitative conversion and high yields were observed with the former. |