Highly photoactive mesoporous F-doped TiO2 with improved physico-chemical characteristics is achieved using modified sol–gel method. The usage of trifluoroacetic as fluorine precursor significantly modifies the morphology, size, pore shape, crystal phase, crystal structure, surface chemical state and to a lesser extent, {1 0 1} and {0 0 1} facets. The accessibility of fluoride ions on TiOTi polymer chains during crystal growth during the sol–gel process remarkably influences the properties of catalyst. To the best of our knowledge, preparation of F-doped TiO2 using modified sol–gel and trifluoroacetic acid are limited, and still not enough. Thus this work provides additional insight by using an approach which is less hazardous, less costly and practical for large scale agile development in the photocatalysis industry.