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Brookite TiO₂ is the most difficult TiO₂ polymorph to synthesize. The available methods in the literature to produce brookite nanostructures mostly use water-based techniques for the preparation of water-soluble Ti complexes first, followed by a hydrothermal growth of the brookite nanostructures. Besides its multi-step nature, achieving a single brookite phase and optimizing the aqueous growth environment are all issues to be hardly controlled. In this work, pure brookite TiO₂ nanorods are synthesized using tetrabutyl titanate Ti(OBu)₄ and Sodium Fluoride (NaF) as precursor materials in a simple non-aqueous one-pot solvothermal process. Alcoholysis of only Ti(OBu)₄ in ethanol resulted in pure anatase nanoparticles, while the addition of NaF was essential to promote the growth of highly pure brookite nanorods. The phase purity is confirmed by X-Ray Diffraction, Raman Spectroscopy, and High-Resolution Transmission Electron Microscopy. The growth mechanism is explained according to the Ostwald’s step rule, where Na⁺ ions are anticipated to have a potential role in driving the growth process towards the brookite phase.