Cationic polymerizations of p-methylstyrene (pMS) with H2O/AlCl3/triphenylamine (TPA) or triethylamine (TEA) initiating system were carried out in mixed solvents of n-hexane and dichloromethane at -80 similar to -50 degrees C. The effects of TPA or TEA concentration, solvent polarity, polymerization temperature and time on monomer conversion, number-average molecular weight (M-n), molecular weight distribution (MWD, M-w/M-n), stereoregulatity and crystallinity of poly(p-methylstyrene) (PpMS) were investigated. The stereospecific cationic polymerization of p-methylstyrene could be achieved and high molecular weight (M-n = 116,000 similar to 436,000 g mol(-1)) polymers with isotactic-rich segments (more than 75% of meso dyad) along macromolecular chains could be successfully synthesized. A possible mechanism for stereospecific cationic polymerization of pMS was proposed. The propagation proceeded via the dominant back-side attack and insertion of monomer from the growing ion paired species. The steric course of propagation was mainly determined by the tightness of the growing ion paired species and steric hindrance in counteranion. The resulting isotactic-rich PpMS could form crystal morphology with 10 similar to 30 mu m in size by flow-induced crystallization under pressure at 180 degrees C. A possible model for the aligning mechanism was sketched to describe crystallization and to explain the multi-melting peaks and lower glass transition temperatures of PpMS. This is the first example of stereospecific cationic polymerization of p-methylstyrene to get crystallizable polymers with such high molecular weights and isotacticity. (C) 2012 Published by Elsevier Ltd.