Adding 2-phenoxyethylamine (POEA) into a CH3 NH3 PbBr3 precursor solution can modulate the organic-inorganic hybrid perovskite structure from bulk to layered, with a photoluminescence and electroluminescence shift from green to blue. Meanwhile, POEA can passivate the CH3 NH3 PbBr3 surface and help to obtain a pure CH3 NH3 PbBr3 phase, leading to an improvement of the external quantum efficiency to nearly 3% in CH3 NH3 PbBr3 LED.