We describe here the use of gold nanoparticles in conjunction with chip-based capillary electrophoresis toimprove the selectivities between solutes and to increasethe efficiency of the separation. We coated the microchannel wall of a microfluidic device with a layer of poly(diallyldimethylammonium chloride) (PDADMAC) andthen collected on it citrate-stabilized gold nanoparticles.The resolutions and the plate numbers of the solutes weredoubled in the presence of the gold nanoparticles. Suchselectivity improvements reflect changes in the observedmobility accrued from interactions of solutes with theparticle surface. The electrochemical detection and thequantitation of the solutes were not effected by thePDADMAC and the gold nanoparticles.