Luminescent CdS nanocrystals embedded in a polystyrene matrix were successfully prepared. The in situ growth of CdS QDs was realized by thermal treatment of Cd bis(thiolate)/polymer foil at different times and temperatures (240∘C and 300∘C) of annealing, in order to evaluate their influence on the quantum dots growth process. As a general trend, the increasing of time and temperature of annealing induces a rise of the CdS nanocrystals size into the polymeric matrix. The size distribution, morphology, and structure of the CdS nanoparticles were analysed with HRTEM and XRD experiments. UV-Vis and PL data are strongly size-dependent and were used to investigate the particles' growth process, too. The CdS nanoparticles behavior in solution indicated a general trend of QDs to aggregation. This predisposition was clearly displayed by DLS measurements.