Macroporous cross-linked organic polymers, based on styrene and divinylbenzene (PS-DVB), are prepared as monolithic stationary phases for capillary electrochromatographic applications. The synthetic strategy, which relies on the semiinterpenetrating polymer network (semi-IPN) approach, is performed through UV-initiated free radical copolymerization of the comonomers in the presence of poly( ε -caprolactone) (PCL) within the confi nes of fused silica capillaries. The characterization of PS-DVB monoliths is carried out at the different stages of the synthesis using a combination of experimental techniques, thus providing information on the chemical and porous structures. All experimental results evidence the sole role of the PCL oligomer as a porogen.have been applied for reversed-phase, [ 4 ] ion-exchange and normal-phase, [ 5 ] chiral, [ 6 ] and hydrophilic interaction liquid chromatography (HILIC) [ 7 ] electrochromatography allowing for the separation of a broad range of molecules such as peptides, [ 8 ] proteins, [ 9 ] enantiomers, and so on. [ 10 ] In most cases, the preparation of polymer-based monoliths relies on thermally or photochemically triggered freeradical copolymerization of monomers in the presence of a porogenic solvent. [ 11 ] Albeit simple, the key challenge for the synthesis of monolithic materials includes the fi ne tuning of pore size distributions in the micrometer range that is essential to permit liquid fl ow through the materials at a reasonable pressure. Smaller pores, in the nanometer range, may be incorporated into the polymer structure to obtain large surface areas. Although both the nature and the amount of the pore-forming agent allow for the control of porous properties associated with the resulting monolithic materials through the solvation of growing polymer chains in the course of the polymerization process, implementation of hyper-cross-linking reaction in the second