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The phases, their lattice parameters and the linear coefficient of the lattice thermal expansion were determined by high-temperature X-ray diffraction between room temperature and the melting point for the system (GaxIn1 − x)2Se3 (1 ≥ x ≥ 0). A wide homogeneity range of zinc blende structure was found in the Ga-rich region when a certain critical temperature was reached. In the In-rich region the alloys were isostructural with γ-In2Se3 at all temperatures, and the linear thermal-expansion coefficient was composition dependent.