The preparation of porous polymethacrylate-based open tubular capilary columns by in-situ copolymerization of octadecyl methacrylate (OMA), and ethylene dimethacrylate (EDMA) in N,N-dimethylformamide (DMF) solvent are proposed. The parameters of the preparation procedure of the stationary phase are discussed in detail. The surface of the cross-section of an open tubular (OT) column by scanning electron microscope (SEM) showed wrinkle configuration, which is expedient to enhance proportion of stationary phase and column capacity. Efficient separation of six alkyl benzene homologous series (namely, toluene, ethylbenzene, propylbenzene, butylbenzene, amylbenzene and hexylbenzene) were performed by CEC using the prepared column, and their elution order was in agreement with their hydrophobicity. So, the OT columns bonded with octadecyl ligands yielded reversed-phase retention behavior toward nonpolar solutes. In addition, the separation of four antiepileptics was also investigated with satisfactory effectiveness. The column efficiency range was 35 300-49 800 plates/m. The results showed that the C-18-OT column of organic matrix for reversed-phase chromatography was successfully prepared via in-situ polymerization in this work. Hereby, this new column thus offers a promising new alternative in OT-CEC and will be useful in separation science.