Ti-41Ni-9Cu shape memory alloy was synthesized by mechanical alloying of pure elemental Ti, Ni, and Cu powders using high-energy ball milling. The qualitative and quantitative phase analyses of the as-milled powders were done by X-ray diffraction (XRD) using Rietveld refinement and the alloys microstructure was studied by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Concerning the results, by milling evolution, the dissolution of the primary materials occurred at different rates and a considerable amount of the amorphous phase as well as B19′-martensite and B2-austenite was created. The formation of Ni solid solution was also evidenced prior to its dissolution. It was found that at sufficient milling time, the mechano-crystallization of the amorphous phase occurred and at the end of milling, the B19′-martensite is the dominant phase of the structure.