We prepared two batches of surface-enriched (with active sites) polymer-supported phase-transfer catalysts (SE-PSPTC) by fixing the crosslinking monomer divinylbenzene (DVB) at 2% (first batch) and 6% (second batch) through a free-radical suspension copolymerization method with vinylbenzyl chloride (VBC; 25%) as a functionality and with styrene (St) as a supporting monomer, followed by the quaternization of the resulting terpolymer beads with triethylamine. The enrichment of the active sites on the surfaces of the beads was accomplished by a surface-grafting technique through the delayed addition of the functional monomer NBC) to the partially polymerized copolymer beads of poly(St/DVB). To bring the active sites fully onto the surfaces, we prepared six different types of terpolymer beads in each batch by varying the partial polymerization time (PPT) of St/DVB-0 h [0 VBC (conventional)), 3 h (3 VBC), 6 h (6 VBC), 9 h (9 VBC), 12 h (12 VBC), and 15 h (15 VBC)-and then gradually adding the functional monomer (VBC) to the partially polymerized poly(St/DVB) system. The resulting terpolymer beads, containing different concentrations of pendant benzyl chloride (-CH2Cl) on the surface in each batch, underwent facile quaternization [-CH2N+(C2H5)(3)Cl-] with an increase in the PPT of St/DVB and remained constant at 12 VBC and 15 VBC. To asses the superiority of the catalysts according to the surface enrichment of the active sites, particularly between conventional (0 VBC) catalysts and other PPT-based SE-PSPTCs, we characterized all the catalysts by estimating the chloride-ion concentration, by using Fourier transform infrared (FTIR), scanning electron microscopy (SEM), EDAX, and ESCA, and by carrying out the dichlorocarbene addition to olefins. The chloride-ion concentration by the Volhard method and the peak intensity of the C-N stretching absorbance concentration, that is, the quaternary onium group in the FTIR spectra of both batches, increased with the PPT of St/DVB in both batches of catalysts. In particular, the chloride concentration of a first-batch catalyst of a representative mesh size ((-)120 + 140) had a twofold enhancement between the conventional catalyst (0 VBC 1.88 m equiv g(-1)) and 9 VBC/SE-PSPTC (3.74 m equiv g(-1)), although the same amount of the functional monomer was added in both preparations. These results showed the higher enrichment of the active site on the surface of 9 VBC, and the same trend was also maintained for second-batch catalysts, regardless of the catalyst mesh size. SEM images of both batches showed that there was higher concentration of nodules [due to the grafting of poly(VBQ] on the surfaces of the beads of 9 VBC/SE-PSPTC and the aforementioned PPT catalysts than on the surfaces of the conventional catalysts (0 VBCs), which exhibited smooth surfaces (because of the simultaneous addition of all three monomers). This observation confirmed the enrichment of active sites on the surfaces. In the EDAX analysis, up to a depth of 0.5-1 mum, the surface chloride concentration increased from 0 VBC to 9 VBC/SE-PSPTC and remained constant in 12 VBC and 15 VBC, first-batch catalysts of a representative mesh size (-120 + 140). The same trend was also observed in second-batch catalysts, indicating the enrichment of the onium group more on the surface in 9 VBC/SE-PSPTCs. The ESCA analysis, to a depth of about 20-30Angstrom, proved that the concentration of covalent chloride on the surface had increased from 0 VBC (15%) to 9 VBC/SE-PSPTCs (29%) and remained constant thereafter in first-batch catalyst; the trend was the same for second-batch catalysts, also confirming the strong evidence of surface enrichment of the active sites. Similarly, the rate constants of different olefin addition reactions catalyzed by both batches of catalysts also increased from 0 VBC to 9 VBC and remained constant with 12 VBC and 15 VBC catalysts. The twofold increase of the rate constants, regardless of the olefins, for conventional catalysts to 9 VIBC/SE-PSPTCs confirmed the enrichment of the active sites on the surfaces. All these experimental observations proved that 50% of the active sites were successfully brought out from inside the poly(St/DVB) networks to the exterior surfaces, although same amount of VBC was added for the preparation of all the catalyst types.