The development of highly efficient blue perovskite light-emitting diodes (PeLEDs) remains a big challenge, requiring more fundamental investigations. In this work, significant photoluminescence enhancement in mixed halide blue perovskite films is demonstrated by using a molecule, benzylphosphonic acid, which eventually doubles the external quantum efficiency to 6.3% in sky-blue PeLEDs. The photoluminescence enhancement is achieved by forming an oxide-bonded perovskite surface at grain boundaries and suppressing electron-phonon interaction, which enhances the radiative recombination rate and reduces the nonradiative recombination rate, respectively. Moreover, severe thermal quenching is observed in the blue perovskite films, which can be explained by a two-step mechanism involving exciton dissociation and electron-phonon interaction. The results suggest that enhancing the radiative recombination rate and reducing the electron-phonon interaction-induced nonradiative recombination rate are crucial for achieving blue perovskite films with strong emission at or above room temperature.