A new and selective sorbent for molecularly imprinted solid-phase extraction (MISPE) was prepared to extract chlorpyrifos (CPF) residue from solutions. The extracted analyte was analyzed by high performance liquid chromotography (HPLC) coupled with photodiode array detection. To synthesize the molecularly imprinted polymers, four different pyrogens (acetonitrile, toluene, dichloromethane and chloroform) were initially studied. CPF was used as the template molecule, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the crosslinker. Thermo-polymerization method was used to produce bulk polymers. In order to determine the medium that enhances the best molecular recognition, the adsorption study of CPF to the MIPs was investigated. Both organic solvents and water were utilized as media. The acetonitrile solvent was finally selected as pyrogen for the synthesis of the polymers and water was chosen as the medium for loading the analytes into the polymers. The selectivity of the MISPE method for CPF and other pesticides in aqueous solution was also assessed.