Polymeric nanocapsules were synthesized by encapsulating extruded vesicles of dimethyldioctadecyl ammonium bromide (DODAB) using a reversible addition-fragmentation chain transfer (RAFT)-based encapsulation approach. Random copolymers containing acrylic acid and butyl acrylate units were first synthesized by RAFT in solution using dibenzyl trithiocarbonate (DBTTC) as the RAFT agent. These anionic copolymer chains were subsequently adsorbed onto the surface of cationic DODA B vesicles and then chain extended to form a polymeric shell by starved feed emulsion polymerization. Cryogenic transmission electron microscopy (cryo-TEM) characterizations demonstrate the successful formation of nanocapsules.