Nickel and titanium alternated nanolayers were deposited from Ti and Ni targets. The multilayer thin films were designed in order to have equiatomic overall chemical composition with a period from 5 to 70 nm. The chemical composition, morphology, structure and phase transformation behaviour were studied. The surface and cross-section morphology of the as-deposited thin films was analysed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The Ni/Ti thin films present in their surface nanograins and for higher periods in cross section it was possible to distinguish the alternated layers and measure their thickness. The structural evolution with temperature was analysed by in-situ hot stage X-ray diffraction (XRD). The as-deposited multilayer thin films exhibit a tendency to a transitory disorder as the period decreases. For the smaller periods a disordered phase forms during the deposition process, while in Ni/Ti multilayers with higher periods this phase is only observed during annealing. By increasing the temperature an exothermic reaction occurs with the formation of the B2-NiTi austenitic phase. In spite of moderate enthalpy of mixing, the multilayers with intermediate modulation period of Ni/Ti films show potential to be used for joining purposes.