A versatile method for the modification of three-dimensionally ordered macroporous (3DOM) highly syndiotactic polystyrene via chloromethylation at the pore walls has been demonstrated. This was followed by reaction with dimethylamine to establish a versatile approach to functionalization of such macroporous polymers. High syndiotacticity of 3DOM sPS is necessary for maintenance of the morphology of the original ordered pore structure after chloromethylation. The relative content of chloromethyl groups was shown to be 1.89 mmol/g3DOM sPS by TG-titration. The functionalized 3DOM sPS was characterized by SEM, FT-IR, and DSC to demonstrate that chloromethylation had occurred at the pore walls and that the dimethylamino moiety had replaced the chlorine atom of the chloromethyl group. DSC examination of the modified polymer indicated that the crystallinity of 3DOM sPS is little affected by functionalization. Thus the excellent properties of sPS are retained by the functionalized material. POLYM. ENG. SCI., 49:223-228, 2009. (C) 2008 Society of Plastics Engineers