We report the synthesis of mesoporous TiO2 nanostructures based on the decomposition of TiOSO4 in aqueous alkaline solution at room temperature, followed by mild thermal treatment (110 °C) in an oven and suitable to yield up to 40 g of product per batch. The duration of the thermal treatment was found to be crucial to control crystalline phase composition, specific surface area, surface chemistry and, accordingly, the photocatalytic properties of the obtained TiO2 nanocrystals. The thorough investigation of the prepared samples allowed us to explain the relationship between the structure of the obtained nanoparticles and their photocatalytic behavior, that was tested in a model reaction. In addition, the advantage of the mild treatment against a harsher calcination at 450 °C was illustrated. The proposed approach represents a facile and sustainable route to promptly access an effective photocatalyst, thus holding a significant promise for the development of solutions suitable to real technological application in environmental depollution.