The diffusion couples for experimental study were prepared by HVOF spraying of nickel and nickel with 20 wt.% of chromium powders onto an aluminium sheet surface. The interfaces with sharp gradients of chemical concentration of these elements were prepared. Annealing at temperatures of 600°C and 630°C, close to the Al + Al3Ni eutectic melting point (639.9°C), with different dwell times were used. During annealing, the reactants diffuse and form layers of Al3Ni2 and Al3Ni intermediate phase compositions. Moreover, nickel without the assistance of chromium diffuses preferably along the grain boundaries into aluminium substrate and produces the strengthening of the substrate by stable Al3Ni and metastable Al9Ni2 particles. The microstructures were obtained by scanning electron microscopy. Layer thickness measurements were realized by means of image analyses. Chemical composition was estimated by energy dispersive microanalysis measurements. According to the results of the analyses performed the average chemical interdiffusion coefficients and Wagner’s integral interdiffusion coefficients were calculated.