This study synthesized the molecularly imprinted polymers by using the molecular structure analogues of α-(OH)-sanshool as the template molecule, 2-Vpy as functional monomer, EDMA as crosslinking agent at the mole ratio of 1:4:20, and then the molecularly imprinted solid-phase extraction (MISPE) was prepared. The optimal sample solvent, drip washing solvent and elution solvent were selected out and the SMIP was used to separate and purify the numb taste components in Zanthoxylum oleoresin, the results show that the SMIP had the especially specific adsorption to the numb taste components which the relative purity of numb taste components can add to 93.66%.