In the present paper, the effect of milling process on the chemical composition, structure, microhardness, and thermal behavior of Ti-41Ni-9Cu compounds developed by mechanical alloying was evaluated. The structural characteristic of the alloyed powders was evaluated by X-ray diffraction (XRD). The chemical composition homogeneity and the powder morphology and size were studied by scanning electron microscopy coupled with electron dispersive X-ray spectroscopy. Moreover, the Vickers micro-indentation hardness of the powders milled for different milling times was determined. Finally, the thermal behavior of the as-milled powders was studied by differential scanning calorimetery. According to the results, at the initial stages of milling (typically 0-12. h), the structure consisted of a Ni solid solution and amorphous phase, and by the milling evolution, nanocrystalline martensite (B19') and austenite (B2) phases were initially formed from the initial materials and then from the amorphous phase. It was found that by the milling development, the composition uniformity is increased, the inter-layer thickness is reduced, and the powders microhardness is initially increased, then reduced, and afterward re-increased. It was also realized that the thermal behavior of the alloyed powders and the structure of heat treated samples is considerably affected by the milling time.