The copolymers of 4-vinylpyridine (4VP), styrene (St) and divinylbenzene (DVB) with varied compositions, P(4VP-St-DVB), were synthesized by suspension polymerization using 2,2'-azobisisobutyronitrile (AIBN) as an initiator. The insoluble (crosslinked) pyridinium-type polymers in benzyl-pyridinium bromide form, which possess various macromolecular chain compositions, were prepared by the reaction of each P(4VP-St-DVB) with benzyl bromide (BzBr), respectively. By using different halohydrocarbon RX in the quaternization of P(4VP-St-DVB), the insoluble pyridinium-type polymers with various pyridinium group structures were obtained. The structures of P(4VP-St-DVB) and its quaternized product Q-P(4VP-St-DVB) were identified by FTIR. The 4VP content in each copolymer P(4VP-St-DVB) was measured by nonaqueous titration; and the pyridinium group content (C-q) in each Q-P(4VP-St-DVB) sample was determined by means of the back titration manner in argentometry and/or the elemental analysis method, respectively. In addition, the particle structure and the surface morphology of the thus-prepared polymer were observed using SEM. According to a series of experimental results, the preparation and characterization of insoluble pyridinium-type polymers are analyzed and discussed. This work can prepare the ground for a study on the antibacterial activity of insoluble pyridinium-type polymers.