A series of novel perovskite single crystals are innovatively grown. Aiming to enhance the luminescence performance, octahedral distortion coregulation via dual strategies for the as-prepared perovskite single crystals is performed. The distortion of the octahedral structure strengthens the electron− phonon coupling and electron localization, resulting in a more stable self-trapped state, which thereby increases the potential for radiative recombination, accompanied by the self-trapped exciton emission. Accordingly, the luminescence spectra of the as-prepared MA 4 In 0.975 Sb 0.025 Br 7 single crystal can cover the 450− 800 nm range, and the photoluminescence quantum yield is up to 81.25%.