Recent developments in the one-step synthesis of structurally controlled hyperbranched polymers (HBPs) in terms of molecular weight, dispersity, number of branching points, branching density, and number of chain-end groups by radical polymerization are summarized. Copolymerization of conventional vinyl monomers and a vinyl telluride, which induces the branching structure, under organotellurium-mediated radical polymerization (TERP) affords HBPs with dendrimer and dendron structures. The same synthetic strategy under atom transfer radical polymerization is also discussed.