Three-dimensionally ordered macroporous(3DOM) syndiotactic poly(p-methylstyrene) (sPPMS) with pore size 170 nm was fabricated by means of silica templates using (dbm)(2)Ti(OPh)(2)/MAO catalytic system. The resulting polymers were characterized by SEM, C-13 NMR, DSC and GPC. The results indicated that the 3DOM sPPMS were highly syndiotactic. GPC curves showed that the 3DOM sPPMS possessed lower Mn and broader MWD compared with bulk one. Meanwhile, DSC results revealed that three 3DOM sPPMS exhibited crystalline form 11, and bulk sPPMS form III. (c) 2005 Elsevier Ltd. All rights reserved.