A SiO 2 –ZrO 2 nanostructured optical fibre is fabricated using the chemical sol–gel method associated to the drawing process; the structural and the waveguiding properties are studied. The refractive index difference (RIP) between the core and the cladding is 0.021 for a 30mol% ZrO 2 – 70mol% SiO 2 core composition. Illumination of the fibre with a supercontinuum source (350–1750nm) shows that the light is guided over this entire range. The measured attenuation losses are 0.7dB/m at a 1064nm wavelength and the calculated cutoff wavelength is 714nm. To control the nanostructure and the geometric parameters of the fibre, a preliminary study of the SiO 2 –ZrO 2 binary system has been done, by X-ray diffraction (XRD), differential thermal analysis (DTA), thermo gravimetric analysis (TGA), transmission electron microscopy (TEM) and scanning electron microscopy (SEM); in addition the evolution of the sol viscosity with the time is studied.