In this work, magnetite-catalyzed Fenton reaction was investigated under UVA irradiation for the degradation of phenol as model compound. Four kinds of magnetite were used having different particle size, surface area and Fe-II content. Different kinetic behaviors were observed, thereby underscoring the strong implications of surface and chemical properties of magnetite. The size and surface area of the particles seemed to be less important, while the Fe-II/Fe-III ratio played some role. Despite the link between magnetite reactivity and its structural Fell content, light-induced reduction of Fe-III to Fe-II was found necessary to promote the Fenton-based reactions. As surface Fe-II may be oxidized or otherwise unavailable, initial photoactivation may be needed to trigger the Fenton reactivity. Two major driving forces were highlighted that account for the photoactivity of magnetite at pH 3: (i) the formation of intermediates such as hydroquinone that are able to reduce Fe-III to Fe-II, and (ii) the accumulation of dissolved Fe due to magnetite dissolution, both in dark and under irradiation. Very interestingly, the photo-Fenton degradation of phenol was also observed under neutral conditions. In this case, for two out of four samples, the degradation rates were quite near those found at pH 3, which is usually reported as the optimum pH value of the process. The magnetite ability to promote photo-Fenton reactions even under circumneutral pH conditions, the limited iron leaching and its easy magnetic separation makes magnetite a promising catalyst in wastewater treatment applications. (C) 2014 Elsevier B.V. All rights reserved.