Novel reversible networks utilizing photodimerization of crosslinkable anthracene groups and thermal dissociation were investigated. Reversible addition-fragmentation chain transfer polymerization yielded well-defined copolymers with 9-anthrylmethyl methacrylate (AMMA) and other alkyl metha-crylates such as methyl methacrylate (MMA) and 2-ethylhexyl methacrylate (EHMA) having different AMMA compositions. Well-controlled block copolymerization of AMMA and alkyl methacrylates was also successfully accomplished using a trithiocarbonate-terminated poly(alkyl methacrylate) macro-chain transfer agent. The anthracene-containing copolymers showed reversibility via crosslinking based on photodimerization with ultraviolet irradiation and subsequent thermal dissociation. (C) 2016 Wiley Periodicals, Inc.