We report for the first time the multi-gram scale solution growth of α-aluminium fluoride trihydrate (α-AlF₃·3H₂O) nanorods (NRs) under low supersaturation conditions, and their conversion to porous β-AlF₃ NRs. Electron microscopy analysis shows that the NRs yielded from the optimized conditions have an average length of 1.9 μm and diameter of 223 nm. Nanoparticle morphology can also be achieved by tuning the supersaturation through several experimental parameters such as [Al³⁺] and [HF]/[Al³⁺] and H₂O/2-propanol vol. ratio. Moderate thermal treatment of the as-synthesized α-AlF₃·3H₂O NRs in air atmosphere (5 h at 500 °C) results in pure β-AlF₃ porous NRs, which may be useful as catalysts.