In this study, block copolymers of PS-b-PMSMA with various molecular weight were synthesized by atom transfer radical polymerization (ATRP). GPC analysis showed that the molecular weight distribution of the prepared PS-b-PMSMA could be controlled to be lower than 1.3 for the case of molecular weight less than 30,000. The chemical structures of the amphiphilic block copolymers of PS-b-PMSMA were well identified by FTIR. SEM showed that the spherical micelles and compound micelles were produced in hybrid films. The EDX analysis indicated that the nano-sized CdS particles have been successfully prepared in the PS-b-PMSMA composite films. The diameter of CdS particles calculated from Brus formula was about 4-5 nm. PL analysis revealed that the λmax of emission of the prepared composite materials had a red-shift as the CdS particle size increased.