Four methacrylate ester-based monolithic columns for capillary liquid chromatography (CLC) were prepared by radical polymerization with ammonium peroxodisulfate (3 columns) and by thermal initiation (1 column). The polymerization mixture consisted of butyl methacrylate (BMA) and ethylene glycol dimethacrylate (EDMA), propan-1-ol, butane-1,4-diol, water, and ammonium peroxodisulfate as initiator. It was necessary to add N,N,N′,N ′-tetramethylethylenediamine (TEMED) to the polymerization mixture to activate the reaction. The amount of initiator and activator was optimized to attain quantitative polymerization. The reproducibility of three columns prepared at ambient temperature was studied. The most efficient column with HETP of 29 μm for uracil was compared to the monolithic column prepared by thermal initiation with α,α′-azobisisobutyronitrile (AIBN). The efficiencies of all the test columns were characterized by van Deemter curves. Their total porosities were calculated from the retention time of uracil. Walters indices of hydrophobicity (HI) were calculated from the retention factors of anthracene and benzene. The columns prepared by both methods are comparable in their selectivities and efficiencies. They show the same characteristics because their total porosities and Walters indices of hydrophobicity are consistent. However, the preparation of monoliths using ammonium peroxodisulfate was less demanding, because polymerization was possible at ambient temperature.