TiO 2 /Luffa composites have been successfully prepared via a sol-gel method from the hydrolysis of a precursor of TiO 2. The possibility to use Luffa fibers as biotemplate to self-support hierarchical TiO 2 macrostructures has also been tested with success. The photocatalysts and the TiO 2 /Luffa composites were characterized by X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, FT-IR, and UV-visible spectroscopy. The photocatalytic activities have been investigated in the photodegradation of methanol, chosen as model molecules for VOCs in air. The reactions have been followed by IR-operando spectroscopy. TiO 2 /Luffa composites exhibited a good stability and photocatalytic activity under UV light irradiation, giving rise to a new generation of green photocatalysts, easy to shape and manufacture, for the photodegradation of organic pollutants.