Photoinduced charge transfer and separation in chemically hybridized CdS-PVK nanocomposites is investigated by steady-state and time-resolved photoluminescence as well as photoconductivity measurements. The chemically hybridized CdS-PVK composites display a longer luminescence lifetime than the pure CdS nanoparticles. At the same time, they show an enhanced photoconductivity as compared with PVK. It is also found that the chemically hybridized Cd-PVK nanocomposites exhibit a higher photoconductivity than the CdS/PVK nano-blends at the same molar ratio. The photoluminescence and photoconductivity results are explained by fast interfacial charge transfer between the Q-CdS and PVK.