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In this work, the thermal stability of Cu-In alloys with 45.0 and 41.2 at.% In nominal compositions was investigated by differential scanning calorimetry (DSC), scanning electron microscopy, wavelength dispersive spectroscopy, and in-situ synchrotron x-ray powder diffraction (S-PXRD) over a temperature range from 25 up to 400 °C. The studied samples are mainly composed of a Cu 11 In 9 phase together with minor amounts of the B phase (based on the NiAs-Ni 2 In type structure) and, in one of the samples, with a minor amount of pure In. No evidence of the Cu 10 In 7 (41.2 at.% In) phase was detected, not even in the sample with 41.2 at.% In nominal overall composition. The combined use of the S-PXRD and DSC techniques allowed us to identify two phase transitions involving the Cu 11 In 9 phase, one of them corresponding to the g 0 Ð B þ Cu 11 In 9 reaction at T = 290 °C and the other to the peritectic g 0 þ L Ð Cu 11 In 9 reaction at T = 311 °C.