This study investigated the methylene blue (MB) decolorization through heterogeneous UV-Fenton reaction catalyzed by V-Ti co-doped magnetites, with emphasis on comparing the contribution of V and Ti cations on improving the adsorption and catalytic activity of magnetite. In the well crystallized spinel structure, both Ti4+ and V3+ occupied the octahedral sites. Ti4+ showed a more obvious effect on increasing specific surface area and superficial hydroxyl amount than V3+ did, resulting in a significant improvement of the adsorption ability of magnetite to MB. The UV introduction greatly accelerated MB degradation. And magnetite with more Ti and less V displayed better catalytic activity in MB degradation through heterogeneous UV-Fenton reaction. The transformation of degradation products and individual contribution from vanadium and titanium on improving adsorption and catalytic activity of magnetite were also investigated. These new insights are of high importance for well understanding the interface interaction between contaminants and metal doped magnetites, and the environmental application of natural and synthetic magnetites. (C) 2011 Elsevier B.V. All rights reserved.