Copper selenides are attractive materials for high-temperature thermoelectric applications. They exhibit remarkably enhanced thermoelectric properties originating from their superionic liquid character. In this work, the synthesis of Cu-Se compounds is investigated using mechanical alloying, aiming to obtain the Cu 2 Se phase and modify the crystal structure by annealing at high temperatures and quenching. In the first part, Cu-Se powders are prepared at various milling times. They are characterized regarding their structure, morphology and composition by X-ray diffraction analysis and scanning electron microscopy. After 2.5 h of synthesis, α-Cu 2 Se and β-Cu 2 Se was attained in the powder, with the former having the highest percentage contribution. The crystallite size of these phases was calculated to be in the range of 17.0-19.6 nm. The synthesized powder consisted of grains with dimensions from nanometers to micrometers and their aggregates. A trace of a possibly surficial layer of copper oxide was also detected on the sample. In the second part of this study, the optimum synthesized powder was subjected to 2 h of annealing at 650 °C, followed by quenching. According to X-ray diffraction analysis, the percentage contribution of the thermoelectrically inferior α-Cu 2 Se phase increased being the vast majority of the material and almost eliminated β-Cu 2 Se. The crystallite size was calculated to be in the range of 31.2-34.5 nm. Overall, the desired Cu 2 Se compound can be obtained by the mechanical alloying technique as α-and β-phase, and the crystal structure can be modified by annealing under appropriate conditions.