The high efficiency of polymer light-emitting diodes (PLED) with ternary electron injection layers (EILs) including tetraoctylammonium bromide (TOAB), poly (vinylpyrrolidone) (PVP) and polyethylenimine (PEIE) to comprise PEIE-PVP-TOAB (E-P-T) EIL that has been achieved and well-studied via mixture design. In the unary system, TOAB can construct interfacial dipole via self-assembly crystallization atop various conjugated polymer surfaces to elevate the vacuum level of cathode. When employing three EILs as ternary system, the electrical property of PLED was further improved. The optimum luminescence efficiency respectively are 13.4 cd/A and 13.5 cd/A for T-P-D and E-P-T based PLED. In the ternary system (E-P-T), PEIE, PVP, and TOAB respectively provides electron injection, hole blocking, and polymer intersecting in the ternary based devices. The intersecting between PEIE and PVP by TOAB was evidenced by roughness change from AFM images.