This chapter describes stereoregulation methods for free-radical polymerization based on (I) rationally designed monomers, (II) chiral initiators and chain-transfer agents, (III) reaction conditions (monomer concentration, temperature, solvent), and (IV) template molecules.Method I includes polymerization of bulky methacrylates giving highly isotactic polymers. Method II in volves menthol-based peroxides and thiols that can control helicity in 1-phenyldibenzosuberyl methacrylate polymerization. Method ΙII was effective for triphenylmethyl methacrylate polym erization where isotacticity content of resulting polymer was con trollable in the range >99-64%. Method IV was realized for methacrylic acid polymerization in the presence of amine com pounds.Stereoregulation by free-radical polymerization has been achieved only in limited cases. On the other hand, stereochemical control of polymerization is an important topic in macromolecular chemistry because polymer properties are often significantly influenced by main-chain configuration and conformation, and various effective methods and catalysts for stereoregulation have been found for anionic, coordination, and related polymerizations (7,2). However, because free-radical polymerization is applicable to much wider range of monomers and generally less expensive compared with the other polymerizations (J), it will be a powerful and practical tool for pro ducing various types of polymers having ordered structures once effective methods for stereocontrol are developed. This article describes our recent studies on configurational and conformational control of free-radical polymerization.