In this paper, influences of poly (N-vinyl-carbazole) (PVK) on the emission properties of zinc selenide (ZnSe)-based organic–inorganic heterostructure devices have been studied. A broad band emission peak at 443nm, with shoulders at 520 and 595nm, was observed from ITO/PVK(80nm)/ZnSe(120nm)/Alq 3 (15nm)/Al under electric fields and it consisted of emissions from PVK, ZnSe and Alq 3 layers. Therefore, a charge carrier injection luminescence in ZnSe layer is suggested. By changing the thickness of PVK layer and/or ZnSe layer, the roles of PVK in the device were discussed.