Metal halide perovskites have been focused as a candidate applied as a promising luminescent material for next-generation high-quality lighting and high-definition display. However, as perovskite films formed, high density of defects would be produced in solution processing inevitably, leading to low exciton recombination efficiency in light-emitting diodes (LEDs). Herein, a facile and novel self-passivation strategy to inhibit defect formation in perovskite films for constructing high-performance LEDs is developed. For the first time, we introduce 1,4,8,11-tetraazacyclotetradecane (cyclam) in perovskite precursor solution, and it spontaneously passivates defect states of CsPbBr3-based perovskites by coaction between amine and uncoordinated lead ions during spin-coating without an anti-solvent process. Furthermore, as a delocalized system, cyclam also possesses chemical properties that facilitate exciton transportation. The proposed passivation strategy boosts the external quantum efficiency from 1.25% (control device) to 16.24% (cyclam-passivated device). Furthermore, defect passivation is also conductive to reduce LED degradation paths and improve device stability as the extrapolated lifetime (T50) of LEDs at an initial brightness of 100 cd/m2 is increased from 0.9 to 127 h. These findings indicate that the introduction of cyclam is highly effective to enhance the performance of LEDs, and such a strategy in effectively reducing the defects could be also applied in other perovskite-based devices, such as lasers, solar cells, and photodetectors.