Substituted styrenes with linear alkyl substituents (C-6 to C-12) at the Para position on the ring were synthesized and polymerized using the (Me)(5)CpTi(OMe)(3)/MAO catalytic system. Increased polymerization activities were observed for longer alkyl group (>C-6) substituted styrenes; all resulting polymers were highly syndiospecific (>99% rr) regardless of alkyl chain lengths. Syndiotactic poly(p-alkylstyrene)s were characterized by SEC, H-1 and C-13 NMR, DSC, and X-ray diffraction. No melting transition was observed for polymers prepared from p-methyl-, p-n-hexyl, and p-n-octylstyrenes. Side-chain-induced crystallization was observed for linear C-10 and C-12 alkyl-substituted polystyrenes (T-m approximate to 90 degreesC). The T-g decreased with an increase in the length of alkyl side chain up to C-8 length; above C-10 side-chain length, the T-g slightly increased. The T-g's of syndiotactic poly(p-n-alkylsyrene)s were significantly higher than those reported for the corresponding nontactic analogues.