Acrylate-based monolithic capillary columns were prepared from fused-silica capillaries using UV photopolymerization. The effect of the pretreatment of the capillary wall surface before polymerization was investigated and several procedures were compared. The columns were characterization by van Deemter curves and SEM imaging. The results indicated that a pre-silanization of the capillary wall in order to introduce methacrylate groups at the wall surface gave similar efficiencies but more homogeneous structures than when the silanization agent was introduced in the polymerization mixture. The conditioning of the capillary before silanization, especially the conditions of basic rinsing was also an important factor. The effect of the dose of UV light that was applied for the polymerization had also been investigated. The results demonstrated that the irradiation energy is a critical parameter. The minimum energy threshold required to obtain a suitable monolith was 3 J/cm(2) and the maximum was around 12 J/cm(2). A higher energy destroys the monolith. Within the convenient range of energy, the columns had the same efficiency and a good structure as seen by SEM imaging. Using the optimized procedure for the pretreatment and an adequate energy, the column-to-column repeatability was found good (n = 12). The repeatability was obtained for the plate height at two velocity values, the retention factor and the electroosmotic mobility with RSD values below 10.