The two-dimensional organic-inorganic hybrid perovskites demonstrate significant potential for use in photodetectors and white light-emitting diodes. In this study, we successfully synthesized pure and Mn2+-doped (PEA)2PbBr4 perovskite via rapid crystallization. The morphology, structure, magnetic properties, and optical characteristics of them were comprehensively characterized. The unusual behavior of free exciton emission is mainly attributed to electron-phonon coupling and negative thermal quenching effects. The self-trapped exciton emission results from self-trapped excited states and electron-phonon coupling. Moreover, energy transfer phenomena are observed between free exciton emission, self-trapped exciton emission, and Mn2+ emission. These findings offer valuable insights into the luminescence mechanism of two-dimensional layered perovskites.