The synergistic effect between fluorine and hydrogen in hydrogenated F-doped TiO2 photocatalysts is evaluated for the photocatalytic degradation of atrazine. The interaction between fluorine and hydrogen species in hydrogenated F-doped TiO2 overcomes the limitations of individual F-doped TiO2 and hydrogenated TiO2 photocatalyst properties. Hydrogenated F-doped TiO2 is photo-active under UV, visible and infrared light illumination with efficient electrons and holes separations. The optimized concentration of surface vacancies and Ti3+ centers coupled with enhanced surface hydrophilicity facilitates the production of surface-bound and free hydroxyl radicals. The surface of the catalyst contains =Ti-F, =Ti-OH, =Ti-O-vacancy and =Ti-H bonds as evidenced by XPS, Raman, FTIR and HR-TEM analysis. This combination also triggers the formation of new Ti3+ occupied states under the conduction band of hydrogenated F-doped TiO2. Moreover, the change in the pore structure from cylindrical to slits and larger surface area facilitates surface charge interactions. The thermal stability is also enhanced and a single anatase phase is obtained. The size of the particles of hydrogenated F-doped TiO2 is also uniform with defined and homogeneous crystal structure. This synergetic effect between fluorine and hydrogen opens up new alternatives in improving the properties of TiO2 and its photocatalytic activity. (C) 2016 Elsevier B.V. All rights reserved.