Alignment layer plays a critical role on liquid crystal (LC) conformation for most LC devices. Normally, polyimide (PI) or polyvinyl alcohol (PVA), characterized by their outstanding thermal and electrical properties, have been widely applied as the alignment layer to align LC molecules. Here, we used a semi-conductive material poly(N-vinylcarbazole) (PVK) as the alignment layer to fabricate the cholesteric liquid crystal (CLC) device and the polymer-stabilized cholesteric liquid crystals (PSCLC)-based infrared (IR) reflectors. In the presence of ultraviolet (UV) irradiation, there are hole–electron pairs generated in the PVK layer, which neutralizes the impurity electrons in the LC–PVK junction, resulting in the reduction in the built-in electric field in the LC device. Therefore, the operational voltage of the CLC device switching from cholesteric texture to focal conic texture decreases from 45 V to 30 V. For the PSCLC-based IR reflectors with the PVK alignment layer, at the same applied electric field, the reflection bandwidth is enhanced from 647 to 821 nm, ranging from 685 to 1506 nm in the IR region, which makes it attractive for saving energy as a smart window.