For the first time, conventional and controlled miniemulsion polymerization of vinyl acetate (VAc) was performed using gamma radiation as alternative source of initiation. Reversible addition-fragmentation chain transfer/macromolecular design via interchange of xanthates (RAFT/MADIX) technique was applied to control the polymerization process. For this purpose, S-2-cyano-2-propyl-O-ethyl xanthate (CTA) was used as chain transfer agent. To illustrate the advantages of using gamma radiation instead of other initiation sources, we compared gamma radiation and the 2,2'-azobis(isobutyronitrile) (AIBN) as initiators in the polymerization mediated by RAFT/MADIX technique. Compared with conventional miniemulsion polymerization, the controlled polymerization process allowed obtaining monomodal molecular weight distributions and a significant control over the molecular weight distribution. The miniemulsions showed colloidal stability during polymerization and stable latices were obtained in a short reaction time with high conversion. Gamma radiation demonstrated to be a better initiator than AIBN for the miniemulsion polymerization of VAc, mediated by RAFT/MADIX. (C) 2016 Elsevier Ltd. All rights reserved.