In recent years, there has been an increasing interest in exploiting fluorous derivatives/moieties for applications that are not only related to reaction mixture purification issues and catalyst recycling, but to confer unique/improved properties to materials. Herein we will focus on the recent advances of fluorous chemistry in material sciences, with special emphasis on applications in organic electronics, crystals/metal–organic frameworks (MOFs) engineering and surface modification chemistry, in particular SiO₂ surfaces. By selecting major contributions in these areas, we wish to highlight the benefits imparted by the introduction of fluorous tags within/onto materials, such as favouring the self-organisation of charge-carrier compounds in bulk heterojunctions, improving the hydrophobicity and/or stability of coordination polymer networks, facilitating solid-state structural rearrangement of large magnitude within crystals or the modification of surfaces through adsorption processes.