AbstractThe synthesis of 6‐vinylchrysene (1) starting from chrysene is described. The study of the polymerizability of1by conventional radical, cationic, and Ziegler‐Natta procedures indicates the tendency of1of give head‐to‐tail polymeric products with a similar degree of polymerization independent of the catalytic system. Copolymers of1with optically active (−)‐menthyl acrylate (2), (−)‐menthyl methacrylate (3), and (S)‐4‐methyl‐1‐hexene (4), were also prepared. No apparent copolymerization of1with optically active alkyl vinyl ethers occurred by cationic initiation. Spectroscopic and chiroptical properties are presented to support the formation of copolymer macromolecules. Finally, the differential dichroic absorption measurements allow one to stress that in optically active vinylaromatic copolymers the extent of preferential asymmetry, induced by the dissymmetric field of units derived from the optically active nonaromatic comonomer, increases with increasing bulkiness and polarizability of the