A simplified approach to synthesize nonparticulate (continuous or monolithic) beds with embedded vancomycin chiral selectors for capillary electrochromatography is proposed. In the present approach, N,N'-diallyltartardiamide monomer with diol functionality is used, which can be readily converted to aldehyde groups via periodate treatment. Parallel to the activation of the polymeric matrix for covalent attachment of vancomycin, the periodate treatment has shown secondary effects on the polymeric bed morphology, namely the increase of the average pore size and porosity of the skeleton. Inversed size-exclusion chromatography was applied to characterize porosimetric properties of the capillary columns before and after the periodate treatment. Electroosmotic and enantioselective properties of the nonparticulate beds synthesized are presented. The approach is of more general interest attaching different affinity groups to the polymeric matrix and/or enhancing the accessibility to the active sites, for instance, in the molecular imprinting technique.