RAFT copolymerization of beta-pinene and maleic anhydride was successfully achieved for the first time, using 1-phenylethyl dithiobenzoate as chain transfer agent in a mixed solvent of tetrehydrofuran and 1.4-dioxane (1:9, v/v) at a feed molar ratio of beta-pinene to maleic anhydride as 3:7, and the alternating copolymer was prepared with predetermined molecular weight and narrow molecular weight distribution. Furthermore, using former alternating copolymer as a macro-RAFT agent, block copolymer poly(beta-pinene-alt-maleic anhydride)-b-polystyrene was synthesized in a chain extending with styrene. Hydrolysis of this block copolymer under acidic conditions formed a new amphiphilic block copolymers poly(beta-pinene-alt-maleic acid)-b-polystyrene whose self-assembly behaviors in aqueous solution at different pH were investigated through SEM and DLS. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1422-1429