The performances and spectroscopic properties of CdSe/ZnS quantum dot light-emitting diodes (QD-LEDs) with inserting a thickness-varied 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi) layer between the QD emission layer and 4,4-N,N-dicarbazole-biphenyl (CBP) hole transport layer (HTL) are studied. The significant enhancement in device peak efficiency is demonstrated for the device with a 3.5 nm TPBi interlayer. The photoluminescence lifetimes of excitons formed within QDs in different devices are also measured to understand the influence of electric field on the QD emission dynamics process and device efficiency. All the excitons on QDs at different devices have nearly the same lifetime even though at different bias. The improvement of device performance is attributed to the separation of charge carrier accumulation interface from the exciton formation zone, which suppresses exciton quenching caused by accumulated carriers.