A number of polymer butyl methacrylate-co-ethylene dimethacrylate and lauryl methacrylate-co-ethylene glycol dimethacrylate monolithic phases within capillary columns were produced with integrated gold nano-particle (GNP) modified segments for on-capillary extraction and subsequent separation of biomolecules. Photo-masking and photo-grafting techniques were used to produce an aminated zone at the start of the polymer monolithic col-umns, which was then converted to a nano-agglomerated section using GNPs, followed by the otherwise unmodified monolith. The extent of amination was verified using scanning capacitively coupled contactless conduc-tivity (sC 4 D) and the C 4 D profiles of modified monoliths monitored throughout the entire fabrication process, as a quality control technique. Two approaches to monolith amination were compared for achieving maximum GNP cov-erage, using surface photo-grafting of either vinyl azlactone or glycidyl methacrylate, prior to reaction with ethylenediamine. The modified monolithic columns were applied to the on-column trapping and subsequent reversed-phase separation of protein standards.