Self-organized TiOF2 nanotubes have been synthesized by a one-pot solvothermal method. Different solvent ratios have been used during material preparation. When choosing the equal ratios of acetic acid and trifluoroacetic acid (TFA) as the solvent, uniform TiOF2 nanotubes were obtained. It is found that the solvent ratios alter their crystalline nature and surface morphology. X-ray diffraction (XRD) pattern indicates that the sample is pure and single-crystalline in nature. Scanning electron microscopy (SEM) morphology points out that the TiOF2 nanotubes with a length of approximately 2–3 μm, which composed of self-assembled nanorods. This distinct construction is advantageous to enhance the photocatalytic hydrogen (H2) evolution under UV–vis irradiation. Photocatalytic examination reveals that the TiOF2 nanotubes have a high photocatalytic H2 evolution rate (~800 μmol h−1 g−1) than other attempted candidates. The excellent photocatalytic H2 evolution attributes to the tube-like morphology and large separations of charge carriers.