The optical and electronic structures of poly (N-carbazole) (PVK) blend with poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) and polyvinylpyrrolidone (PVP) in the same composition were investigated. Polymer coating was carried out using doctor blade technique on a glass substrate. Uv-vis and photoluminescence spectrum revealed that there are significant different results obtained between PVK, PVK:PVP and PVK:PVDF-HFP. The electronic parameters such as absorption edge (Ee), allowed direct bandgap (Ed), allowed indirect bandgap (Ei) and Urbach edge (Eu) were calculated by using Tauc/Davis-Mott Model. The value of Ee and Ed for PVK and PVK:PVDF-HFP almost same but there was significant different value between Eu and Ei.