Olive mill wastewater (OMW) was treated by photocatalysis using TiO2 under UV irradiation on the laboratory scale. The chemical oxygen demand, the coloration at 330 nm, and the level of phenols all showed decreases which, after a 24-h treatment, reached 22%, 57% and 94%, respectively. The differences between these three values indicate the persistence of colourless, non-phenolic compounds. Application of the novel Fictitious Atomic-Group Separation method showed an increase in carbon oxidation state and confirmed that the attack primarily concerns, aromatic moieties. A fine spectroscopic study revealed the occurrence of three successive phases during the degradation process, thought to correspond to three different categories of molecules in the OMW and the presence of pectin compounds. (C) 2007 Elsevier Ltd. All rights reserved.