TiO2 materials were prepared by sol-gel method and then impregnated with sulfuric acid and calcined using different temperatures and atmosphere (air and nitrogen). Systematic variation of these two experimental parameters makes possible to modulate the amount of surface sulfur from the impregnation procedure. The best photocatalyst for liquid phenol degradation was obtained after calcination at 700 degrees C in air, while gas toluene degradation optimum performance is obtained by calcination at 700 degrees C in nitrogen from 500 degrees C. Structural analysis of these materials by XRD, micro-Raman spectroscopy and FE-SEM shows that once calcined at 700 degrees C the material was a well-crystallized, high surface area anatase structure in all cases. The surface characterization by MR and XPS confirms the presence of a higher amount of sulfur species and acidic OH groups in samples partially calcined in nitrogen, and a low XPSO/Ti-atomic ratio with the 0 Is peak shifted to higher binding energies (1.8 vs. 2 +/-0.1 and 530.4 eV vs. 529.8 eV, respectively. against the reference materials) for samples calcined at 700 degrees C, temperature at which most of sulfate species have been evolved. The paper presents an attempt to correlate the contribution of the observed structural defects within the anatase sub-surface layers and surface acidity to the different photoactivity behaviour exhibited for phenol liquid phase and toluene gas phase photodegradation. (C) 2009 Elsevier B.V. All rights reserved.