Luminescent oxidised porous Si is produced by rapid thermal annealing of the anodised material in a dry oxygen ambient. Its light-emitting properties are studied by both photoluminescence and cathodoluminescence methods. The structure of the oxidised material is examined by transmission electron microscopy, while its oxygen content is determined by X-ray microanalysis. These investigations show that crystalline Si nanostructures remain in the oxidised porous material and account for its luminescence properties. The work demonstrates that the speculated importance of either Si-based amorphous phases or the interesting material, siloxene, in this regard is unrealistic.