In the present work, a GCMS method coupled with Molecular imprinting technique was developed for the simultaneous determination of five organophosphorus pesticide residues (i.e., diazinon, malathion, phosphamidon, isofenphos-methyl and quinalphos) in environmental water. In order to obtain a highly selective recognition of OPPs, we synthesized molecularly imprinted polymers (MIPs) using malathion 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 specificity of MIPs and non-imprinted polymers were investigated. The use of MISPE improved the accuracy and precision of the GCMS method. The recoveries of OPPs extracted from water sample at a 1μg/mL spike level were in the range of 82%~97%. The results showed that MIPs enable the selective extraction of OPPs successfully from water sample, and demonstrated the potential of MISPE for selective and cost-effective sample pretreatment.