In this work, we introduced chiral cations into the achiral two-position layered perovskite system for the first time to form an alloyed system that still retains a clear layered structure. In addition, in order to explore the potential photoelectric properties of the alloyed system, manganese ions were doped into the alloyed system. The XRD pattern shows that the steady-state absorption and emission spectra of the alloyed system have a large structural distance, while the doped manganese system exhibits a two-color photoluminescence phenomenon. In addition, combined with time-resolved fluorescence and testing, the photoluminescence characteristics and ultralong lifetime of Mn-doped samples were further characterized. The exciton band structure of the lead halide perovskite framework can be adjusted through this design strategy. Mn2+ ions can form characteristic energy levels in the host system and then energy transfer of excitons occurs, which is of great significance for the development of new functional and high-efficiency photoluminescent materials.