Abstract Titanium dioxide is a widely studied material with well-known applications for anatase and rutile phases. Moreover, brookite, another polymorph, which is more difficult to obtain, has caught scientific community interest, especially for photocatalysis applications. Among many methodologies for TiO2 synthesis, the hydrothermal method stands out, with the possibility of controlling different parameters that lead to a specific phase composition, allowing selective polymorphic obtainment. This method was used to synthesize TiO2 with different anatase/brookite ratios, by the use of different synthesis conditions as pH of the suspension, sodium salt concentration, and temperature, resulting in anatase-brookite photocatalyst with brookite composition ranging from 0 to 35%. The materials were characterized by X-ray diffraction, infrared spectroscopy, Raman spectroscopy, particle size measurement, and scanning electron microscopy. Photocatalysts with the highest brookite amount showed the best photocatalytic results for Remazol golden yellow (RNL) dye decolorization. Moreover, the short-range disorder also played an important role in photocatalytic behavior.