AbstractQuasi‐two‐dimensional (quasi‐2D) perovskites, consisting of multi‐quantum wells (MQWs) separated by organic intercalating cations, exhibit high luminescence efficiency while the photophysical processes involved remain partially obscure due to the uncertainty of the MQWs structure. Herein, a synergetic dual‐additive strategy is adopted to prepare quasi‐2D perovskite films, where 18‐crown‐6 and tris(4‐fluorophenyl)phosphine oxide are utilized to suppress the formation of low‐dimensional perovskites, diminish defect density, and enhance photoluminescence quantum yield to 93.7%. Notably, a long‐lived delayed component, spanning hundreds of microseconds, is identified for the first time in perovskite emitters, which correlates with exciton dissociation and recombination, and the differences in temperature‐dependent radiative lifetime of the delayed components match with the luminescence properties. Finally, benefiting from lower trap density and more efficient energy‐funneling, green PeLEDs treated with dual additives have achieved a high external quantum efficiency of 28.9% and a commendable operating half‐lifetime of 17.8 h at an initial brightness of 500 cd m−2. The observation of the long‐lived delayed components, coupled with insights into exciton dissociation, provides a profound and comprehensive understanding of the fundamental carrier behavior in perovskite emitters and establishes a direct correlation between the properties of perovskite emitters and their photophysical processes.