Mixture of nickel and titanium powders were milled in planetary mill under argon atmosphere for 100 hours at room temperature. Every 10 hours the structure, morphology and chemical composition was studied by X-ray diffraction method (XRD), scanning electron microscope (SEM) as well as electron transmission microscope (TEM). Analysis revealed that elongation of milling time caused alloying of the elements. After 100 hours of milling the powders was in nanocrystalline and an amorphous state. Also extending of milling time affected the crystal size and microstrains of the alloying elements as well as the newly formed alloy. Crystallization of amorphous alloys proceeds above 600°C. In consequence, the alloy (at room temperature) consisted of mixture of the B2 parent phase and a small amount of the B19' martensite. Dependently on the milling time and followed crystallization the NiTi alloy can be received in a form of the powder with average crystallite size from 1,5 up to 4 nm.