We have applied secondary ion mass spectroscopy (SIMS) to the detection of chemical species on outer-most surfaces of polymers. Copper deposited in vacuo on polyvinylalcohol (PVA), polyethyleneterephtalate (PET) and nylon 6, 6' was found, by XPS, to react with the functional groups of the polymers to form Cu-0 (PET), Cu-N (Nylon 6, 6') etc. In static-SIMS spectra of copper-deposited polymers, metallized cluster ions, assigned to [Cu-OC]+, [Cu-OCO]+, [Cu-N]+, were detected. Structures of these cluster ions were dependent on the chemical species, and thus it is suggested that the functional groups of interest could be distinguished from other species on the same surfaces by using this technique.