The first attempts at the synthesis of an indium corrole compound were synthesized in the late 80s, but it has not been possible to obtain and characterize such complex completely, and the indium part of metallocorrole’s periodic table remained unfilled. In this work, an efficient insertion of indium into the 5,10,15-tris(pentafluorophenyl)corrole was achieved. The obtained 5,10,15-tris(pentafluorophenyl)corrolatoindium(III) derivatives has been successfully characterized by relevant analytical techniques and some photophysical and electrochemical features were studied and investigated for the first time. As a novel research, ¹⁹F-¹⁹F COSY NMR technique was employed for the first time in corrole chemistry and the obtained results were further compared to the geometry-optimized molecular structure via density functional theory (DFT) calculations.