This work reports on a facile approach to the synthesis of highly branched polymers by the homopolymerization of commercially available divinyl benzene (DVB) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The presence of RAFT agents allows conversions as high as 68% before cross-linking, instead of 15% for conventional free radical polymerization (FRP). The study extends this new approach by synthesizing starlike block copolymers of methyl acrylate (MA) and DVB by exploiting the living characteristic offered by RAFT polymerization. The resulting highly branched DVB polymers are used to produce in situ cross-linked polymeric particles following thermal stimuli. In addition, we exploit the large number of residual double bonds in the highly branched p(DVB) to further functionalize the polymer via thiol-ene click chemistry.