LAUSR

2D organic–inorganic hybrid perovskites (OIHPs) show obvious advantages in the field of optoelectronics due to their high luminescent stability and good solution processability. However, the thermal quenching and self‐absorption of excitons caused by the strong interaction between the inorganic metal ions lead to a low luminescence efficiency of 2D perovskites. Herein, a 2D Cd‐based OIHP phenylammonium cadmium chloride (PACC) with a weak red phosphorescence (ΦP < 6%) at 620 nm and a blue afterglow is reported. Interestingly, the Mn‐doped PACC exhibits very strong red emission with nearly 200% quantum yield and 15 ms lifetime, thus resulting in a red afterglow. The experimental data prove that the doping of Mn2+ not only induces the multiexciton generation (MEG) process of the perovskite, avoiding the energy loss of inorganic excitons, but also promotes the Dexter energy transfer from organic triplet excitons to inorganic excitons, thus realizing the superefficient red‐light emission of Cd2+. This work suggests that guest metal ions can induce host metal ions to realize MEG in 2D bulk OIHPs, which provides a new idea for the development of optoelectronic materials and devices with ultrahigh energy utilization.