Abstract: A porous polymethacrylate ester-based capillary monolithic column was prepared using in situco-polymerizing butyl methacrylate(BMA) and ethylene dimethacrylate(EDMA) in binary porogenic solvent 1,4-butanediol and 1-propanol.A series of preliminary experiments and orthogonal experiments were carried out,and demonstrated that the ratio between 1,4-butanediol and 1-propanol was a significant factor.Under the optimized mass ratio of 1∶3,the best synthetic polymers were achieved.The column exhibited a uniform structure,good permeability,reproducibility and stability with RSD less than 8.5%,which proved that the polymerization condition was satisfactory.Alkylbenzenes were analyzed to evaluate this monolithic column with CEC method,and the separation of alkylbenzenes was mainly based on typical reversed-phase chromatographic retention mechanism.The theoretical plate number of benzene was 22 400 and the resolutions of alkylbenzenes were more than 4.0.Therefore,the synthetic monolith can be successfully applied to separate neutral small molecules.