Novel self-illuminated smart windows were fabricated consisting of Cu-doped ZnS (ZnS:Cu) powder and polymer-dispersed liquid crystal (PDLC). This smart window shows not only switchable transparency but also self-illumination without any attachable luminous body. Its electro-optical characteristics, transmittance, and luminance were investigated in relation to various applied voltages and composition ratios. The optical transmittance and luminous intensity increased with increasing applied voltages. However, the optical transmittance decreased with increasing ZnS:Cu powder content. One of the self-illuminated smart windows, which was fabricated with 9 wt% of ZnS:Cu, achieved the optical transmittance of 60.5% (at 550 nm) and the luminance of 11.0 cd/m² at 100 V. This smart window could be used as a normal switchable smart window in daytime and light-emitting signage at night.