Molecular imprinting technique offers a means of producing practical materials that are able to recognize a certain molecule in terms of shape, size and chemical functionality. In order to obtain a highly selective recognition of organophosphorus pesticides (OPPs), we synthesized molecularly imprinted polymers (MIPs) using pirimiphos-methyl as the template, methacrylic acid as the monomer and ethylene glycol dimethacrylate as the crosslinker. After polymerization, molecularly imprinted solid-phase extraction (MISPE) was used for the selective preconcentration of OPPs. The preparation methods and synthesis conditions of MIPs were discussed, and the specificity of MIPs and nonimprinted polymers were investigated. The results showed that MIPs enable the selective extraction of pirimiphos-methyl successfully from water sample, and demonstrated the potential of MISPE for selective and cost-effective sample pretreatment.