This paper describes the comprehensive fabrication of monolithic materials for use as stationary phases in capillary liquid chromatography. Several columns were synthesized in the confines of 320 µm i.d. fused-silica capillaries by single-step in situ copolymerization of benzyl methacrylate and ethylene dimethacrylate (EDMA). The polymerization procedure was optimized by varying the reaction time within the range of 0.5-20 h, and by changing the composition contents of the polymeric mixture. The EDMA content showed a predominant influence on the characteristics of the columns and hence, on their chromatographic properties. The optimum value of the thermal initiator corresponded to 5 mg/mL. Changes of the porous, hydrodynamic properties and morphology of the prepared columns were thoroughly investigated and characterized. Different solvents were used as the mobile phase to demonstrate that the resulting monoliths exhibited good permeability and mechanical stability, whereas swelling and shrinking behaviors were observed and discussed. The efficiency and performance toward different sets of analytes were obtained; mixtures of aromatic hydrocarbons and phenolic compounds were successfully separated and evaluated, and adding tetrahydrofuran to the mobile phase showed improvement in both resolution and peak shapes. The characteristics of the columns were also checked in terms of repeatability and reproducibility.