AbstractMetal halide perovskites are emerging as promising semiconductors for cost-effective and high-performance light-emitting diodes (LEDs). Previous investigations have focused on the optimisation of the emissive perovskite layer, for example, through quantum confinement to enhance the radiative recombination or through defect passivation to decrease non-radiative recombination. However, an in-depth understanding of how the buried charge transport layers affect the perovskite crystallisation, though of critical importance, is currently missing for perovskite LEDs. Here, we reveal synergistic effect of precursor stoichiometry and interfacial reactions for perovskite LEDs, and establish useful guidelines for rational device optimization. We reveal that efficient deprotonation of the undesirable organic cations by a metal oxide interlayer with a high isoelectric point is critical to promote the transition of intermediate phases to highly emissive perovskite films. Combining our findings with effective defect passivation of the active layer, we achieve high-efficiency perovskite LEDs with a maximum external quantum efficiency of 19.6%.