A passive layer, of several thousand A thickness, formed on a polycrystalline nickel electrode, has been examined using secondary ion mass spectrometry (SIMS) by spottering with a 5.5 keV, 13μA·cm−2,40Ar+ primary beam. Concentration profiles were detived by monitoring the intensities of atomic and molecular mass peaks as a function of sputtering time (i.e. depth). Nickel was present throughout the layer but not as the element since the relative intensities of the Ni + (n=1, 2, 3, 4) peaks, constituting part of its fingerprint spectrum, differed from those in the fingerprint spectrum of elemental nickel. These values were eventually reached, signifying piercing of the layer and thus providing a means of estimating its thickness. Imaging of58Ni+ showed the presence of nickel in at least two different modifications in the layer, both with higher Ni+ yields than the bulk nickel. Their fractional coverages were estimated from the images taken at various depths. The resulting profile of the Ni+ originating from one of these modifications was found to be proportional to the16O− profile, indicating that these ions originate from the same molecule. This example demonstrates the advantage of combining different SIMS modes (viz. depth profiles, fingerprint spectra and imaging) in tackling certain analytical problems.