Whether in catalysis, biology or the protection of the environment, fluorinated functional materials are emerging as important chemical tools to achieve improved performance and higher stability under a variety of conditions. Providing a distinct increase in molecular hydrophobicity, fluorination allows easy tuning of a material's hydrophilic–lipophilic balance (HLB), in particular with sol–gel materials obtained by polycondensation of fluorinated precursors. Reporting on recent remarkable achievements, this review attempts to show the large unexplored potential of these materials.