Mn-doped TiO2 materials synthetized by the sol-gel method were obtained and tested in the photocatalytic hydrogen production from a methanol-water solution. The Mn amount was varied between 1.0-10.0%wt. Powder X-ray diffraction patterns and Raman spectra of the synthesized solids showed the anatase as the predominant crystalline phase. A high specific surface area was found in the Mn-doped sol-gel catalysts between 88-136 m(2)/g while in bare TiO2 sample 64 m(2)/g only. Mn-doped TiO2 solids evaluated in the production of H-2 showed higher photoactivities (1376 mu mol h(-1)g(-1) for 1.0%wt. Mn and 1736 mu mol h(-1)g(-1) for 5.0%wt. Mn) in comparison with the bare TiO2 semiconductor (264 mu mol h(-1)g(-1)). This improvement in photoactivity is suggested as a combination of charge separators Mn2+, Mn3+ and Mn4+ which can act simultaneously as electron and hole traps respectively. The synergetic effect between the manganese oxidation states and electrons transferred from methanol toward TiO2 particles favored the H-2 production. (C) 2016 Elsevier B.V. All rights reserved.