An acrylate monolith has been synthesized into a cyclic olefin copolymer microdevice for reversed-phase electrochromatography purposes. Microchannels, designed by hot embossing, were filled up with an acrylate monolith to serve as a hydrophobic stationary phase. A lauryl acrylate monolith was formulated to suit the hydrophobic material, by implementing 100% organic porogenic solvent. This new composition was tested in capillary prior to its transfer into the microfluidic device. Surface functionalization of the cyclic olefin copolymer surface was applied using UV-grafting technique to improve the covalent attachment of this monolith to the plastic walls of the microfluidic chip. The on-chip performances of this monolith were evaluated in detail for the reversed-phase electrochromatographic separation of polycyclic aromatic hydrocarbons, with plate heights reaching down to 10 microm when working at optimal velocity.