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The prospects of near- and supercritical water for treatment of the inner surfaces of fused silica capillaries have been tested employing an in-lab-assembled apparatus. Unlike all other agents used for the purpose, water cannot introduce any undesirable heteroatoms to the treated surface. Theoretical background for this work comes from the well-known fact that water near its critical point can solubilize silica. The results show that depending on the temperature, water flow rate, flow mode, and exposure time, high-temperature water has wide-ranging effects on both the surface roughness and the internal diameter profile along the length of the treated capillary. By judicious selection of the operating conditions, tapered capillaries of various profiles for applications in electromigration techniques can be prepared with relatively high reproducibility. The water-treated fused silica capillaries with uniform internal diameter appear to be useful for preparation of monolithic silica capillary columns.