Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to analyse the interface between a non-organofunctional silane and three different metal substrates (aluminium, zinc and an aluminium-zinc alloy). Ion etching using Ga+ ions was used to expose the interfacial region. Ion fragments from the samples were examined carefully where supposed metal-oxygen-silicon ion fragments should appear in the mass spectra. From high mass resolution spectra it was concluded that there exists an AlOSi+ ion fragment at nominal mass m/z = 71 amu on the aluminium and aluminium-zinc alloy substrates and a ZnOSi+ ion fragment at nominal mass m/z = 108 amu on the zinc and aluminium-zinc alloy substrates. These results are further enhanced by the fact that the characteristic ion pattern of ZnOSi+-type ion fragments, composed of different naturally stable zinc and silicon isotopes, in the mass range m/z = 108-112 amu showed the expected relative peak height relations. The presence of these metal-oxygen-silicon ion fragments is a strong indication that chemical interaction between the silane and the metal substrates exists and that the nature of this interaction is due to the formation of a covalent bond between the silane and the metal substrate. Copyright © 2001 John Wiley & Sons, Ltd.