CdS nanocrystals were synthesized in N, N-dimethylformamide solution of poly(styrene-co-maleic anhydride) random copolymer through the reaction of thiourea with cadmium acetate. The resulting random copolymer/CdS nanocrystal composites obtained under different reaction times or cadmium acetate concentrations were very stable and gave a bright photoluminescence emission under UV irradiation at room temperature. A variety of techniques, including UV–vis spectroscopy, photoluminescence spectroscopy and transmission electron microscopy, were employed to characterize the morphological structure and photoluminescence properties of the CdS/poly(styrene-co-maleic anhydride) copolymer nanocomposites obtained.