Vacuum deposition offers precise thickness control and avoids issues such as solvent incompatibility and interlayer dissolution. Despite these advantages, perovskite light-emitting diodes (PeLEDs) fabricated via this method show lower efficiency due to uncontrolled crystal growth and defects. We report a NaF-stacked CsPbBr3 architecture combining coevaporation of CsPbBr3 with sequential NaF evaporation, producing a stacked structure unattainable via solution processing. NaF interlayers provide surface passivation, restrict grain growth to nanograins that enhance exciton binding, and promote (112) orientation via <1% lattice match with NaF(100). We further introduce dual-side guanidinium bromide (GABr) passivation, in which a bottom GABr layer survives perovskite deposition to passivate Pb0 defects, and a top GABr layer is added after. This dual passivation is unattainable in solution processing. Green PeLEDs with the NaF-stacked, GABr-passivated emitter exhibit an external quantum efficiency (EQE) of 7.21% and luminance of 35,289 cd/m2, highlighting vacuum-based structural engineering as a path to improved PeLEDs.