The sol–gel chemistry of titanium-based oxide prepared in a fluorinated medium leads to an oxy-hydroxyfluorinated framework owing to the occurrence of both hydrolysis and fluorolysis reactions. Here, a systematic study was carried out to investigate the impact of the sol–gel synthesis parameters on the reaction of titanium alkoxides and HF. This study provides comprehensive insights into the sol–gel process in a fluorinated medium. Depending on the extent of fluorination, two types of structures can be stabilized including an anatase Ti1–x–y□x+yO2–4(x+y)F4x(OH)4y and a fluoride-rich hexagonal-tungsten-bronze (HTB) Ti1–x□xO1–4x(F,OH)2+4x phases, where □ refers to titanium vacancies. The reactivity of titanium alkoxide in alcohol toward HF has been shown to mostly depend on the solvent characteristics highlighting an alcohol interchange reaction between the titanium precursor and the solvent. Increasing the fluorine concentration leads to a structural change from the anatase to the fluoride-rich HTB phase, ...