Polymer-supported phase transfer catalysts with active sites mostly on the surface were prepared by suspension copolymerization of styrene (St), divinylbenzene (DVB), and vinylbenzyl chloride (VBC) with AIBN, followed by the quaternization of the resulting copolymer beads with triethylamine. Active sites on the surface were achieved by the delayed addition of functional monomer (VBC) to the partially copolymerized St/DVB. Polymer beads enriched with active sites were characterized by SEM, EDAX, FTIR, and ESCA The electron micrographs showed that the exterior surface of delayed-addition functional monomer catalysts (type 1) has a large number of nodules attached to the surface compared to the smooth surface exhibited by the conventional type 2 catalyst upon the simultaneous addition of all three monomers. In the EDAX analysis up to a depth of 100 Angstrom, the surface chloride of type 1 peak intensity is greater (compared with type 2), indicating the -CH2Cl enrichment on the surface. In FTIR, the peak intensities of the C-N stretching (quaternary onium group) in type 1 are greater than those of type 2, confirming the evidence of more quaternization on the surface than in the bulk. From ESCA analysis to a depth of about 30 Angstrom, it was found that type 1 (beads) contains 26% and type 2 contains 14% of covalent chloride on the surface, which strongly supports the grafting of VBC on St/DVB. In the estimation found by the Volhard method, type 1 has 4.73 m eq g(-1) and type 2 has 2.29 m eq g(-1) of ionic chloride, thus supporting the surface grafting of VBC. The catalytic activity of these two different catalysts was tested by studying the reaction, that is, the C-alkylation of phenylacetone. The rate constants of this reaction for type 1 are almost twofold greater than those of type 2, a finding that could uphold the preceding experimental observations. (C) 2000 John Wiley & Sons, Inc.