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The thermochromic phase transformations that occur in one-dimensional Ta2O5 nanorods were analysed at elevated temperatures ranging from 300 to 750 K. X-ray photoemission spectroscopy data revealed not only the electronic structures and chemical properties of the one-dimensional Ta2O5 nanorods, but also their stoichiometric Ta and O compositions. High-temperature X-ray diffraction data revealed complex and polymorphic thermochromic phase transformations of the α(1 0 11), α(200), α(2 0 10), β(3 11 1) and β(2 21 1) lattice planes in the one-dimensional Ta2O5 nanorods, which incorporate β to α (β–α), β to β (β–β), α to α (α–α) and α to β (α–β) phase transitions. The thermochromic phase transformations between α- and β-phase crystals can be explained by a shift in 2θ and expansion of the d spacing of the lattice planes.