The viability of static secondary ion mass spectrometry (S-SIMS) for selected applications of nanoscale analysis has been investigated, focusing on nanofibres produced by electrospinning (ES) as a test case. The samples consist of non-woven nanowebs of which the individual fibres have diameters in the range of 100 nm. Use of solutions with functionalised polymers or polar additives potentially allows the surface composition to be tailored as a function of the application. So far nanowebs are primarily characterised by morphological examination. This paper describes the first detailed characterisation of molecular composition at the surface of nanofibres electrospun from poly(ε-caprolactone) (PCL) solutions in acetone containing 0–15 mol% (relative to PCL) of cetyltrimethylammonium bromide (CTAB). Application of S-SIMS to nanowebs has allowed mass spectra to be recorded containing the major diagnostic ions of both components. Their relative intensities point to surface enrichment and depletion of the polar CTAB additive relative to the PCL matrix for samples electrospun from solution containing low and high CTAB concentrations, respectively. Copyright © 2005 John Wiley & Sons, Ltd.