The ability of polymer dispersed liquid crystals (PDLC) smart window to electrically control the visible and near infrared light transmissions aids to reduce the artificial lightning, heating and cooling loads in the built environment. This study presents a complementary coupling of nitrogen-doped carbon quantum dot (N-CQDs) based waveguide with PDLC smart window device that selectively harvests the ultraviolet light (UV) and near UV light for electrical energy generation without competing for the visible and near-infrared light. The hybrid device can be switchable between transmissive and opaque light scattering state while simultaneously generating electrical energy. Spectral characteristics of the light transmitted through the device confirm that UV photons are completely harvested while most of the visible and near-IR photons are transmitted. The colorimetry analysis of waveguide-coupled PDLC devices is done to realize their compatibility with visual comfort of individuals residing in the building with such windows. We eventually demonstrate that strong scattering effect during the OFF state of waveguide-coupled PDLC device is responsible for its improved optical and power efficiencies (similar to 4.52% and similar to 2.49% respectively) as compared to that in the ON state of PDLC.