Luminescent CdS nanoparticles immobilized on copolymer microspheres were produced by the chemical precipitation of poly(St-co-GMA-IDA)–Cd²⁺ (PSG–Cd²⁺) complexes. PSG latex was prepared by the soap-free emulsion copolymerization of styrene (St) and 2-methacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester (GMA-IDA). GMA-IDA chelating groups within copolymer latex have coordination sites for chelating metal ions, at which CdS particles were grown. The presence of ethanol as a cosolvent improved both the particle monodispersity and the surface charge. Fourier transform infrared (FT-IR) spectroscopy spectra were obtained to elucidate the characteristics of GMA-IDA in the PSG latex. The size distribution, morphology and structure of CdS nanoparticles were measured by transmission electron microscope (TEM) and x-ray diffraction (XRD) analysis. The growth kinetics of CdS nanoparticles were studied by TEM and obtaining photoluminescence (PL) spectra. The size and morphology of CdS particles were influenced by the amount of the chelating, iminodiacetic acid group on the surface of the copolymer microsphere, the concentration of Cd²⁺ ions and the pH. The PSG-A3–CdS sample with [Cd²⁺]/[GMA-IDA] = 1/6, pH = 3.5, which was formed from ultrafine CdS particles with mean diameters below 5 nm immobilized on the surface of copolymer microspheres, emitted photons with a higher energy than other samples in this investigation.