In this study, a new process for preparation of CdS/polymer nanocomposite films using a new amphiphilic oligomer chain (Urethane Acrylate Nonionomer: UAN) is presented. UAN chains have hydrophilic polyethylene oxide segments and polypropylene oxide-based hydrophobic segments as part of the same backbone. In addition, these chains also have reactive vinyl groups at their hydrophobic segments. For the preparation of CdS nano-colloid solutions, UAN chains acted as a stabilizer for CdS nanoparticles dispersed in a solvent. For the fabrication of CdS/polymer nanocomposite films, UAN chains in CdS nano-colloid solutions were polymerized through reactions between their vinyl groups, resulting in the formation of CdS nanoparticle dispersed films swollen by the solvent. The nature of the solvent used strongly influenced the size of the CdS nanoparticles, which was confirmed by UV absorption spectra, PL emission spectra and TEM images. Smaller sized CdS nanoparticles were formed in higher polar solvents such as DMAc and methanol, which can be explained by the higher solubility of UAN chains and the more effective dissociation and stabilization of cadmium salts and CdS nanoparticles by UAN chains in the polar solvent.