Nanostructured tungsten oxide synthesized from SiO2 templates (SBA-15 and KIT-6) has been used for NO2 gas sensing. Chromium has been added as catalytic additive to WO3 in order to enhance sensor response. Several techniques have been used for identifying both additive location in the tungsten oxide matrix and its oxidation state. Raman spectroscopy confirmed the presence of terminal chromium-oxygen bonds at the material surface. Besides, X-ray photoelectron spectroscopy showed chromium peaks attributable to Cr(III) species. Electrical behavior of pure WO3 has found to be highly dependent on the nanostructure type, i. e. 2D SBA-15 and 3D KIT-6 replicas. Chromium addition diminishes response time and improves sensor response at low NO2 concentrations. Electrical differences due to WO3 nanostructure disappears as a result of additive introduction in the material.