The influence of the iron chemical nature contained in ilmenite (FeTiO3) upon the activity and stability of these materials as catalysts for CWPO-Photoassisted process under LED light (lambda: 405 nm) were evaluated. Raw ilmenite was treated with H-2 within the range 25-1000 degrees C in order to partially reduce iron oxides to Fe(0). The catalysts were characterized by N-2 adsorption/desorption, TXRF, XRD and XPS analysis. The co-presence of different iron species (Fe(0), Fe(II) and Fe(III)) along with the light effect over material surface, led to an increase of H2O2 decomposition rate into HO center dot and, therefore, a higher oxidation rate. In all case, after total H2O2 depletion, a complete phenol degradation and a 95% TOC conversion was reached in batch at pH(0) = 3 and 50 degrees C using the stoichiometric H2O2 dose (14 mol H2O2/mol phenol) and 10 W m(-2) LED light. Long-term continuous experiments were carried out to assess the stability and the lifetime of the catalyst. The higher reduction degree led to a higher organic matter mineralization but also to a higher leaching of active phase around 3% of the total iron amount in ilmenite. Nevertheless, catalyst deactivation seems to be related to the oxidation of iron on the catalyst surface. (C) 2016 Elsevier B.V. All rights reserved.