We have synthesized several star-branched polymers having poly(1,4-divinylbenzene) (PDVB) segment(s) by quantitatively linking the 1,1-diphenylethylene-stabilized living anionic PDVB with the chain-(alpha-phenyl acrylate)-functionalized polymers. The synthesized polymers were the A(3) regular star PDVB, A(2)B, AB(2), ABC, ABCD, and A(4)B mu-star polymers. The A arm is the PDVB segment, while the B, C, or D arm is either a polystyrene, poly(methyl methacrylate), poly(alpha-methylstyrene), or poly(2-vinylpyridine) segment. These polymers are the first successful highly reactive PDVB-containing well-defined star-branched polymers, whose pendant vinyl groups are capable of undergoing various postfunctionalization reactions to introduce additional functionalities.