A series of quaternary Ni–Al–Me–C (Me=Ti, Nb or V) alloys and two Ni–Al–Nb alloys from various areas of the Ni–Al phase diagram were prepared by the mechanical alloying (MA) method starting from pure powder mixtures. X-ray diffraction and differential scanning calorimetry were used to investigate the powder alloys. It was found, that MA results in the formation of partially ordered metastable B2-type solid solutions in the case of carbon-free systems. On the other hand, the presence of carbon in the powder alloy results in the formation of ordered intermetallic phase and carbide during the thermal treatment. The grain size of carbide and intermetallic phase were kept within the nanosize range even after heating up to 700°C.