We report the synthesis and characterization of a series of novel diblock copolymers, poly(cholesteryl methacrylate-b-2-hydroxyethyl methacrylate) (PCMA-b-PHEMA). Monomers, cholesteryl methacrylate (CMA) and 2-(trimethylsiloxy)ethyl methacrylate (HEMA-TMS), were prepared from methyacryloyl chloride and 2-hydroxyethyl methacrylate, respectively. Homopolymers of CMA, PCMA, with well-defined molecular weights and polydispersity indices (PDI), were prepared by reversible addition fragmentation and chain transfer (RAFT) method. Precursor diblock copolymers, PCMA-b-P(HEMA-TMS), were synthesized using PCMA as macromolecular chain transfer agent and monomer, HEMA-TMS. Product diblock copolymers, PCMA-b-PHEMA, were prepared by deprotecting trimethylsilyl units in the precursor diblock copolymers using acid catalysts. Detailed molecular characterization of the precursor diblock copolymers, PCMA-b-P(HEMA-TMS), and the product diblock copolymers, PCMA-b-PHEMA, confirmed the composition and structure of these polymers. This versatile synthetic strategy can be used to prepare new amphiphilic block copolymers with cholesterol in one block and hydrogen-bonding moieties in the second block. (c) 2008 Wiley Periodicals, Inc.