Main-chain-functionalized poly(L-lactide) (PLLA) with pendant unsaturations was synthesized through a one-pot postpolymerization procedure with the PLLA homopolymer as the starting material. The material was functionalized through a-hydrogen abstraction by a sterically hindered strong base, lithium diisopropylamide, followed by the addition of an acid chloride. Two different acid chlorides were examined, lauroyl chloride as a concept electrophile and oleoyl chloride to provide the pendant unsaturations. The semisolvated system, together with branching reactions from the alpha position of the acid chloride, yielded a high molar amount of the incorporated reactant in the material. The unsaturations were preserved under the chosen conditions and the material exhibited surfactant-like properties in blends with oleic acid and PLLA. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012