The increasing demand for more efficient and brighter thin-film light-emitting diodes (LEDs) has driven research into three-dimensional (3D) perovskites, which exhibit high charge mobilities and low quantum efficiency droop. To improve LED efficiency, it is crucial to minimize nonradiative recombination while promoting radiative recombination. Various passivation strategies have been used to reduce defect densities in 3D perovskite films, but the slow radiative recombination has limited the photoluminescence quantum efficiencies (PLQEs) to less than 80%, resulting in external quantum efficiencies (EQEs) of less than 25%. This study presents a dual-additive crystallization method that enables the formation of highly efficient 3D perovskites, achieving an exceptional PLQE of 96%. The approach promotes the formation of tetragonal FAPbI3 perovskite, which effectively accelerates radiative recombination. As a result, perovskite LEDs with a record peak EQE of 32.0% are achieved, with the efficiency remaining greater than 30.0% even at a high current density of 100 mA cm−2. The fabrication process involves preparing a precursor solution using 1-aminopyridinium iodide (PyNi), 5-aminovaleric acid (5AVA), formamidinium iodide (FAI), and PbI2. The dual-additive perovskite film exhibits a higher PLQE compared to the control sample, which only has a PLQE of about 70%. Time-resolved photoluminescence (TRPL) measurements show that the dual-additive perovskite has accelerated photoluminescence decay, indicating enhanced radiative recombination. The enhanced PLQE is attributed to increased radiative recombination rates, both excitonic and bimolecular, rather than decreased nonradiative recombination rates. Structural characterization using grazing-incidence wide-angle X-ray scattering (GIWAXS) reveals that the dual-additive perovskite film has a higher proportion of the tetragonal phase, which is associated with a higher exciton binding energy (Eb) of 13.9 meV. This increased Eb leads to higher population of excitons in the excited states, enhancing radiative recombination. The study demonstrates that the dual-additive method can significantly improve the efficiency and brightness of perovskite LEDs, paving the way for advancements in next-generation display and lighting technologies.The increasing demand for more efficient and brighter thin-film light-emitting diodes (LEDs) has driven research into three-dimensional (3D) perovskites, which exhibit high charge mobilities and low quantum efficiency droop. To improve LED efficiency, it is crucial to minimize nonradiative recombination while promoting radiative recombination. Various passivation strategies have been used to reduce defect densities in 3D perovskite films, but the slow radiative recombination has limited the photoluminescence quantum efficiencies (PLQEs) to less than 80%, resulting in external quantum efficiencies (EQEs) of less than 25%. This study presents a dual-additive crystallization method that enables the formation of highly efficient 3D perovskites, achieving an exceptional PLQE of 96%. The approach promotes the formation of tetragonal FAPbI3 perovskite, which effectively accelerates radiative recombination. As a result, perovskite LEDs with a record peak EQE of 32.0% are achieved, with the efficiency remaining greater than 30.0% even at a high current density of 100 mA cm−2. The fabrication process involves preparing a precursor solution using 1-aminopyridinium iodide (PyNi), 5-aminovaleric acid (5AVA), formamidinium iodide (FAI), and PbI2. The dual-additive perovskite film exhibits a higher PLQE compared to the control sample, which only has a PLQE of about 70%. Time-resolved photoluminescence (TRPL) measurements show that the dual-additive perovskite has accelerated photoluminescence decay, indicating enhanced radiative recombination. The enhanced PLQE is attributed to increased radiative recombination rates, both excitonic and bimolecular, rather than decreased nonradiative recombination rates. Structural characterization using grazing-incidence wide-angle X-ray scattering (GIWAXS) reveals that the dual-additive perovskite film has a higher proportion of the tetragonal phase, which is associated with a higher exciton binding energy (Eb) of 13.9 meV. This increased Eb leads to higher population of excitons in the excited states, enhancing radiative recombination. The study demonstrates that the dual-additive method can significantly improve the efficiency and brightness of perovskite LEDs, paving the way for advancements in next-generation display and lighting technologies.