Abstract: This work concerns the structural evolution of Cu₇₀Nb₂₀Al₁₀ (at%) alloy processed by mechanical alloying using a planetary ball mill in air atmosphere for different times (4 to 200 h). The morphological, structural, microstructural, and thermal behaviors of the alloy were investigated by scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and differential scanning calorimetry. X-ray diffraction patterns were examined using the Rietveld refinement technique with the help of the MAUD software. A disordered FCC-Cu(Nb,Al) solid solution was formed after 8 h of milling. The crystallite size, microstrain, and lattice parameter were determined by the Rietveld method. With increasing milling time, the crystallite size of the final product-ternary-phase FCC-Cu(Nb,Al)-is refined to the nanometer scale, reaching 12 nm after 200 h. This crystallographic structure combines good mechanical strength and good ductility. An increase in microstrain and partial oxidation were also observed with increasing milling time.