The surfactant coverage of minidroplets was tuned by postaddition of more surfactants after preparation of the miniemulsion of styrene. The influence of surfactant coverage on reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization of styrene was investigated. When the surfactant (sodium dodecyl sulfate; SDS) coverage was as low as 40%, two kinds of particles, denoted as polymer and oligomer particles, were formed in the early stage of the polymerization. Polymer chains within two kinds of particles grew in a parallel way during the rest period of the polymerization. The oligomer particles contributed less than 10% to the final monomer conversion but consumed over one in third the original RAFT agent molecules. Oligomer particles were larger in size but much lower in molecular weight. Both the particle size and molecular weight distributions were bimodal. With increase of SDS coverage, the formation of oligomer particles was suppressed. As a result, the nucleation efficiency of the minidroplets was greatly enhanced and the molecular weight and particle size distributions were dramatically narrowed. The formation of the oligomer particles was ascribed to the superswelling occurring in the beginning stage of the polymerization. The experimental observations are in excellent accord to the superswelling theory. Postaddition of surfactant presents a novel method to narrow particle size and molecular weight distributions in RAFT miniemulsion polymerization. (c) 2006 Wiley Periodicals, Inc.