A mixture of elemental Ga and Se with the nominal composition Ga 40Se 60 was submitted to the Mechanical alloying technique and their structural, thermal and optical properties were followed by X-ray diffraction, differential thermal analysis, photoacoustic spectroscopy, UV–VIS‐NIR absorbance spectroscopy and Raman spectroscopy techniques. After 10 h of milling the X-ray pattern showed monoclinic Ga 2Se 3 phase nucleation, which is in the nanometric form, and also a minority amorphous phase. The DSC results showed exothermic reactions between 430 and 720 K attributed to amorphous–crystalline phase transition and structural relaxation of Ga 2Se 3 phase. Based on this a small amount of the as-milled sample was annealed at 723 K. Its XRD pattern showed evidences of grain growth, reduction of the interfacial component, as well as, disappearance of the amorphous phase. The annealing process induced thermal diffusivity increasing, while the optical band gap energy and Raman profile remained practically unchanged.