Co films were selectively deposited as Cu capping layers by chemical vapor deposition technique. X-ray fluorescence spectroscopy determined the Co deposition selectivity as a function of the deposition temperature and substrate materials. Co/Cu interfacial property was characterized and revealed no detectable oxygen at the interface. In addition to electrical resistance measurements of the resulted Cu/low-k interconnects, selectivity of the Co deposition process and property of the resulted Co/Cu interface were further confirmed with time-dependent-dielectric-breakdown and electromigration tests.