This article shows that there is great interest in using an electrochromatographic microchip made of hexyl acrylate (HA) based porous monolith cast within the channel of a cyclic olefin copolymer (COC) device. The monolith is simultaneously in situ synthesized and anchored to the inner walls of the channel in less than 10 min. By appropriate choice of light intensity used during the synthesis, the separation efficiency obtained for nonpolar solutes such as polycyclic aromatic hydrocarbons (PAH) is increased up to 250 000 plates/m. The performance of this HA-filled COC microchip was investigated for a wide range of analytes of varying nature. The reversed-phase separation of four aflatoxins is obtained in less than 2 min. The baseline separation of a mixture of neurotransmitters including six amino acids and two catecholamines is possible thanks to the superimposition of the differences in electrophoretic mobility on the chromatographic process. The durability of the system at pH 13 allows the separation of five biogenic amines and the quantitative determination of two of them in numerous wine samples. The feasibility of on-line preconcentration is also demonstrated. Hydrophilic surface modification of COC channel via UV-photografting with poly(ethylene glycol) methacrylate (PEGMA) before in situ synthesis of HA, is necessary to reduce the adsorption of very hydrophobic solutes such as PAH during enrichment. The detection limit of fluoranthene is decreased down to less than 1 ppb with a preconcentration of 4.5 h on the HA-filled PEGMA functionalized COC microchip.