Multisite modulation for organic-inorganic hybrid metal halides (OIMHs) plays an important role in the optimization of their photophysical performance. Herein, we proposed an organic cation modification strategy on the phosphorus sites based on 1,2-Bis(diphenylphosphino)ethane (DPPE) by a simple one-pot solvothermal method. Three zero-dimensional (0D) manganese-based OIMHs, two novel MdppeMnCl