Polyvinyl alcohol (PVA)-capped CdSe nanoparticles were successfully prepared by a one-step solution growth technique at room temperature and ambient pressure. X-ray diffraction, transmission electron microscopy, infrared spectra, and X-ray photoelectron spectra were used to characterize the final product. The as-prepared CdSe nanocrystals were well dispersed and uniform in shape and the diameter of the particles was confined within 8 nm. Ultraviolet-visible absorption spectra were used to study the confined growth process of PVA-capped CdSe nanoparticles. Photoluminescence measurement showed the near band-edge luminescence of the final product.