Chelating poly(acrylates-co-2-methylacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester) microspheres of diameter 250-310 nm were prepared by the soap-free emulsion polymerization method for varying amounts of GMA-IDA. Then CdS/copolymer composite was generated by chemical deposition on the surface of the copolymer microspheres. By XRD analysis it is found that the chelated CdS nanoparticles are a pure cubic zinc blende structure. The CdS/copolymer composite is examined by UV-vis absorbance, photoluminescence, and TEM observation. Average CdS nanoparticle size calculated from Henglein's empirical curve is in the range of 3.0-8.0 nm and varies according to the GMA-IDA molar ratio during polymerization, pH value during chelation, and postchelation annealing temperature. Higher ratio of chelating group, pH value, and annealing temperature produce larger CdS nanoparticles. As GMA-IDA ratio increases, photoluminescence exhibits a red shift from 510 to 520 nm, photoluminescence increases, and bandwidth decreases. Photoluminescence of the CdS nanoparticle becomes negligible when diameter exceeds 5 nm.