The invention relates to the technical field of solid phase extraction, and particularly discloses a prometryn molecular imprinting solid phase extraction column and an application method thereof. With prometryn as a template, methacrylic acid as a functional monomer, glycol dimethyl methacrylate as a cross-linking agent, azodiisobutyronitrile as an initiating agent, dichloromethane as a solvent, a precipitation polymerization method is adopted to prepare prometryn molecular imprintingpolymeric microsphere; microballoons are uniformly filled in the solid phase extraction column, thus obtaining the prometryn molecular imprinting solid phase extraction column; dichloromethane is utilized as, residuals of simazine, atrazine, szimetrin, propazine, ametryn, terbuthylazine, prometryn and terbutryn in a grain sample are simultaneously enriched and purified by taking a sample solvent and dichloromethane-acetonitrile as a leaching solvent and taking methyl alcohol-water as an eluting solvent, when used together with a capillary electrophoresis multiresidue detection method, the prometryn molecular imprinting solid phase extraction column can simultaneously detect the residuals of the eight herbicideds.