The flash combustion method was used to prepare LiF-doped TiO2 photocatalysts materials using glycine or urea as a fuel with different weight percentage of LiF. The synthesized powders have been characterized by thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) with energy dispersive spectrometer (EDX) analyzer, the specific surface area measurement was performed by BET. The crystallization and the phase transformation anatase-rutile for the powders have been verified by XRD. SEM micrographs for these powders shows the presence of nanoparticles. To investigate the optical band gap of the synthesized samples, UV-Vis spectroscopy was conducted using the diffuse reflectance mode (DRS). The O2-/F- substitution and the presence of Ti3+ centers was confirmed by electron paramagnetic resonance (EPR) analysis. The photocatalytic activity of the TiO2-xLiF powders were evaluated through the photocatalytic degradation of Methylene blue (MB) in water under UV-visible light exposure. The results indicated that during the flash combustion synthesis, the nature of the fuel and the percentage of the doping element led to the presence of different polymorphs of TiO2 which influences the photocatalytic efficiency attributed to the synergistic effect between the two phases (anatase and rutile). The LiF-doped TiO2 powders synthesized by flash combustion in both cases (by using glycine or urea) showed high performance in MB degradation compared to commercial TiO2 and undoped synthesized TiO2 powders, with an optimal degradation of 99 % achieved with 2 wt. % LiF-doped TiO2 using glycine as a fuel and after 6 hours of UV-Vis irradiation.