X-ray photoelectron spectroscopy (XPS) characterization of Nicalon NML 202 was carried out on the desized initial fibre (fibre A), fibre A after treatment with hydrofluoric acid (fibre B) and fibre B oxidized in air at 970 K (fibre C). Non-etched and Ar+-etched fibre bundles were studied. XPS analysis quantitatively fits the chemical analysis of the fibre: the Nicalon fibre is a continuous SiC and SiOxCy tetrahedron network with an excess of carbon and exhibits a silica sheath.