Silica monolithic capillaries (SMCs) were synthesized by a sol-gel process. First, a simplification of the synthesis was proposed by replacing the calcination and the drying steps which can have tremendous effects on chromatographic and physical properties, by a single water or methanol 2 h washing step. The efficiency of such a washing step was demonstrated and the comparison of the chromatographic and electrochromatographic properties between calcined and washed SMCs has shown that such a modification did not impair retention, efficiency, and stability of the monolith. This simplified procedure was carried out to synthesize SMCs with two different skeleton sizes. These capillaries were evaluated in electrochromatography and present high efficiencies (H = 5 mu m) at least equal to the best ones reported in the literature. Furthermore, the influence of the skeleton size on the EOF of the second kind (EOF-2) was investigated with unmodified SMCs used under various experimental conditions including electrical field strength and buffer concentration. The ionic strength of the mobile phase and the applied electrical field that enable this EOF-2 were related to the size of the skeleton which was tuned by the synthesis conditions.