The intermetallic compounds are very interesting in a multitude of structural and functional applications, such as in turbomachines or engine parts, due to their good behaviour at high temperatures, as well as their high resistance to corrosion and oxidation. In the present work, the study of processing of the Ni-Al system intermetallics has been carried out by means of Self-Propagating High–Temperature Synthesis initiated by concentrated solar energy (SHS–CSE). Synthesis by this high-energy exothermic reaction often causes the appearance of porosity, lack of interlayer adhesion, volumetric expansion, and even the total loss of sample shape. To obtain high-quality systems, a study has been carried out on one-layer and multi-layer configurations from powder materials, considering the influence of the heating rate and time. The use of concentrated solar energy has allowed to obtain fully densified nickel parts at 1000°C in just 15 min, compared to the 1325°C and more than 12h required by conventional techniques to obtain lower relative densities (~97%). The best results in multilayer configurations have been achieved in Ni-Ni/Al-Ni system with the synthesis of intermetallic compounds type Ni2Al3, NiAl and Ni3Al. The control of volumetric expansion and porosity, full densified nickel layers perfectly adhered to the interlayer and hardness values up to 900 HV have been obtained in just 2 min. This work highlights the wide possibilities of the use of CSE in metal treatment, which allows efficient and sustainable synthesis of new systems and the improvement of the final properties of the parts.