We report the application of reversible addition-fragmentation chain transfer (RAFT) polymerization using poly(dimethylsiloxane) (PDMS) chain transfer agents toward the synthesis of a variety of diblock copolymers containing tert-butyldimethylsilyl methacrylic (MASi) monomer units. The methodology relies on the synthesis of PDMS monofunctional chain transfer agents easily available in one synthetic step from commercially available hydroxylated PDMSs. The RAFT process enables access to polymer chains with narrow molar mass distributions and high conversions. Data from differential scanning calorimetric measurements revealed that the diblock copolymers exhibited two glass transition temperatures, corresponding to the PDMS- and PMASi-enriched phases, respectively. Copolymerizations of MASi and butyl methacrylate (BMA) within the second block led to immiscible phases with lower glass transition temperatures than PDMS-block-PMASi copolymers. (C) 2013 Elsevier Ltd. All rights reserved.