Three-dimensionally ordered macroporous cross-linked polystyrenes (3DOM CLPS) with 2-mercaptobenzothiazole (MBZ) groups attached directly or via hydrophilic spacer arms to frameworks were prepared for use as heavy metal ion adsorbents. The hydrophilic spacer arms are polyethylene glycol (PEG) chains with three different lengths. The functionalized 3DOM CLPS were characterized by SEM, FTIR, and elemental analysis. The results confirm that the MBZ groups have been introduced onto the pore wall of 3DOM CLPS directly or via PEGs, and the ordered structure was well preserved after functionalization. The functionalized 3DOM CLPS are effective adsorbents for the removal of heavy metal ions from solution, with adsorption capacities ranging from 0.25 to 1.14 mmol/g for silver (I) ions and 0.28 to 0.51 mmol/g for mercury (II) ions, respectively. The introduction of hydrophilic spacer arms between the 3DOM frameworks and the heterocyclic functional groups improves the adsorption capacities and adsorption kinetics. The adsorption capacities increase with the length of spacer arm. After regeneration by washing with acidic thiourea solution, the metal ion adsorption capacities of the regenerated 3DOM materials were on around 90% of the original capacities. POLYM. ENG. SCI., 2012. (C) 2011 Society of Plastics Engineers