Macroporous polymeric monolith bearing thiol-reactive surface functionalities was prepared within micrometer-sized fused silica capillary column by photochemically-driven free radical copolymerization of N-acryloxysuccininimide and ethylene dimethacrylate in the presence of toluene as porogenic solvent, hereafter poly(NAS-co-EDMA), and subsequent surface grafting of allylamine through nucleophilic substitution reaction. The pore surface with pendant allyl moieties was further functionalized via a two-step thiol-ene click reaction with thiol-containing oligo(ethylene glycol) and mercaptoethanol, successively. The surface hydration ability, i.e. hydrophilic character, of the as-obtained monolith was evaluated as a function of the water-content of the liquid fluid environment through electrochromatographic evaluation of the retention properties of the -(O-CH2-CH2)-like surface-functionalized capillary monolith. A major result was that the so called hydrophilic interaction electrochromatographic mode was observed at a given mobile phase composition. An example is given for the separation of phenol-derivatives, with the most hydrophilic one being the most retained. In addition, the hydrophilic interaction based separation allowed for reduced analysis time as compared to the separation observed under reversed-phase separation mode using analogous monolithic stationary phase. Finally, the versatility of the thiol-ene photoaddition approach is demonstrated with an example of C18-like monolith for reversed-phase separation application. (O) 2011 Elsevier Ltd. All rights reserved.