We report the synthesis of CdS quantum dot (QD)–poly(acrylate) nanocomposites using a recently developed catalytic system where activators are generated by electron transfer for atom-transfer radical polymerization (ATRP) in a miniemulsion. The QD surface was functionalized with a tris(alkyl)phosphine, previously modified with an ATRP chlorine initiator, and subsequent controlled polymerization was carried out from the functionalized surface of nanoparticles. The final material showed a high homogeneity and the QDs were evenly dispersed. The optical-absorption edge in the visible spectra of the nanocomposites attests the presence of the CdS QDs. Quantum confinement effects were assigned, though a blue shift in relation to the optical spectrum of the initial QDs has been observed.