In the presence of anhydrous ferric chloride as a Friedel-Crafts catalyst, the posterosslinking reaction of macroporous styrene-divinylbenzene (St-DVB) copolymers synthesized under different conditions was carried out with 1,2-dichloroethane as a solvent. Without an externally added crosslinking agent, the specific surface area and pore volume, for copolymers with different DVB isomers or different DVB contents after reaction, in most cases increased significantly, and the increase was found to be heavily dependent upon the amount of the pendant vinyl groups in the starting copolymers. These results further confirm the role of the pendant vinyl groups in creating new crosslinking bonds in addition to those created by a free-radical crosslinking reaction in the starting copolymers, and an alkylation reaction of the vinyl groups with neighboring aromatic rings is believed to dominate the course of the postcrosslinking at a relatively high level of the vinyl group contents. The synthesis conditions, including the n-heptane content in a mixed diluent and the amount of the diluent, under which the starting copolymers were synthesized, play an important role in the increase of the surface area and pore volume of the copolymers after postcrosslinking. The effect of these conditions is attributed mainly to the swelling ability of the starting copolymers thus obtained in the solvent used for reaction.