Highly efficient vacuum-deposited CsPbBr3 perovskite light-emitting diodes (PeLEDs) are demonstrated by introducing a separate polyethylene oxide (PEO) passivation layer. A CsPbBr3 film deposited on the PEO layer via thermal co-evaporation of CsBr and PbBr2 exhibits an almost 50-fold increase in photoluminescence quantum yield intensity compared to a reference sample without PEO. This enhancement is attributed to the passivation of interfacial defects of the perovskite, as evidenced by temperature-dependent photoluminescence measurements. However, direct application of PEO to an LED device is challenging because of the electrically insulating nature of PEO. This issue is solved by doping PEO layers with MgCl2. This strategy results in an enhanced luminance and external quantum efficiency (EQE) of up to 6887 cd m–2 and 7.6%, respectively. To the best of our knowledge, this is the highest EQE reported to date among vacuum-deposited PeLEDs.