Poly (2-hydroxyethyl methacrylate)-block-poly (3-(methacryloxy)propyl trimethoxysilane) (PHEMA-b-PMPS) was obtained through the reversible addition–fragmentation chain transfer polymerization (RAFT) and analyzed using 1H NMR, FTIR, GPC and DSC techniques. Under the polymerization condition, the Mw/Mn value of the well-defined block copolymers was around 1.1–1.2. These silicon-containing polymers possess many applications. First, this amphiphilic block copolymers shown good ability based on its surface tension control performance. Then, the self-assembly behaviors of block copolymer in the mixed solvents were studied. DLS results have shown that the aggregates could self-assemble into core–shell particles. These core–shell structure and resulting hybrid core–shell nanoparticles were analyzed by TEM. Finally, the biocompatibility of the copolymer hydrogels was verified by in vitro cell viability studies on fibroblasts L929. [ABSTRACT FROM AUTHOR]