AbstractOptically active co‐isotactic copolymers of α‐olefins, like (R)‐3,7‐dimethyl‐1‐octene (1) or (S)‐4‐methyl‐1‐hexene (2), with functional para‐substituted styrenes were obtained by both copolymerization in the presence of Ziegler‐Natta catalysts and by chemical modification of the copolymers of styrene (5) with 1 or 2. By the first mentioned route copolymers of 4‐iodostyrene (3) and propyl 4‐vinylbenzenesulfonate (4) were prepared in satisfying yields. Fractionation by solvent extraction as well as the physical properties of the polymeric products, guarantee for the formation of co‐isotactic copolymer macromolecules. By the other route co‐isotactic copolymers of 1 or 2 with several para‐substituted styrenes (like 4‐halo, 4‐chloromethyl, 4‐diphenylphosphino, 4‐diphenylphosphinomethyl, and 4‐alkylammoniomethyl chloride derivatives) were prepared under conditions which do not give appreciable racemization of the chiral centers present in the main chain as well as in the lateral chain of the starting copolymers of styrene with α‐olefins. The reported data provide a useful way to attain stereoregular and chiral macromolecular materials, bearing either electron donor or chemically active functional groups, inserted in a highly homogeneous conformational environment.