Capillary electrochromatography (CEC) of oligosaccharides in porous polyacrylamide monoliths has been explored. While it is possible to alter separation capacity for various compounds by copolymerization of suitable separation ligands in the polymerization backbone, "blank" acrylamide matrix is also capable of sufficient resolution of oligosaccharides in the hydrophilic interaction mode. The "blank" acrylamide network, formed with a more rigid crosslinker, provides maximum efficiency for separations (routinely up to 350,000 theoretical plates/m for fluorescently-labeled oligosaccharides). These columns yield a high spatial resolution of the branched glycan isomers and large column permeabilities. From the structural point of view, some voids are observable in the monoliths at the mesoporous range (mean pore radius ca. 35 nm, surface area of 74 m2/g), as measured by intrusion porosimetry in the dry state.