Cadmium sulfide (CdS) nanoparticles of three different sizes of 1.49, 2.0, and 2.1 nm were synthesized by the chemical method using thioglycerol as a capping agent. Optical absorption, wide angle x-ray scattering (WAXS), small angle x-ray scattering (SAXS), and high-resolution transmission electron microscopy (HRTEM) measurements revealed that nearly monodispersed particles of high quality could be obtained using a simple and straightforward method used in the present investigation. The nanoparticles were further used to fabricate heterojunctions with poly-phenylene-vinylene (PPV), and currentvoltage characteristics were measured. A large forward current density of 21 mA cm )2 at 1 V is obtained for samples having the smallest average particle size and 13 mA cm )2 for the samples having the largest particle size among the samples investigated.