Monolithic poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) and poly(4-methylstyrene-co-vinylbenzyl chloride-co-divinylbenzene) capillary columns have been prepared and their the surface area increased using hypercrosslinking process. This technique includes solvation with dichloroethane followed by Friedel-Crafts reaction catalyzed by iron trichloride. These monolithic columns were then used for separation in capillary electrochromatographic mode. Although these columns do not contain any ionizable functionalities, adsorption of ions from the buffer solution modifies the surface and affords electroosmotic flow (EOF) in all tested columns. However, the hypercrosslinking leads to a more than 1 order of magnitude large increase in EOF due to a significantly enhanced number of ions adsorbed at the polymer with much larger surface area. For example, hypercrosslinked poly(4-methylstyrene-co-vinylbenzyl chloride-co-divinyl- benzene) affords an EOF of 2.6×10^-8 m²/V.s compared to EOF 1.24 × 10^-9 m²/V.s  found for its non-hypercrosslinked counterpart. The performance of the hypercrosslinked columns is demonstrated with the separation of alkylbenzenes with the best baseline separation achieved in less than 8 min.