Enhancing the injection of electron is an effective strategy to improve the performance of polymer light-emitting diodes (PLEDs). In this work, we reported a 286% improvement in current efficiency (CE) of PLEDs by using double-layered alkali halide electron injection layer (EIL) NaCl/LiF instead of LiF. A significant enhancement of electron injection was observed after inserting the NaCl layer. To understand the mechanism of such improvement, the devices with KBr/LiF and CsF/LiF as EILs were also investigated. Experimental results show that metal cation migrated under the effect of built-in electric field (Vbi), which plays the main role on the improvement of electron injection in PLEDs.