As part of extensive research on the properties of nickel-aluminum alloys, corrosion tests of sintered materials produced by the innovative HPHT/SPS (high pressure, high temperature/spark plasma sintering) method were performed in 0.1 molar H2SO4 acid. The hybrid, unique device used for this purpose (one of only two such devices operating in the world) is equipped with a Bridgman chamber, which allows heating with high-frequency pulsed current and sintering of powders under high pressure in the range of 4–8 GPa and at temperatures up to 2400 °C. Using this device for the production of materials contributes to the generation of new phases not obtainable by classical methods. In this article, the first test results obtained for the nickel-aluminum alloys never before produced by this method are discussed. Alloys containing 25 at.% Al, 37 at.% Al and 50 at.% Al were produced. The alloys were obtained by the combined effect of the pressure of 7 GPa and the temperature of 1200 °C generated by the pulsed current. The time of the sintering process was 60 s. The electrochemical tests, such as OCP (open circuit potential), polarization tests and EIS (electrochemical impedance spectroscopy), were carried out for the newly produced sinters and the results were compared with the reference materials, i.e., nickel and aluminum. The corrosion tests showed good corrosion resistance of the produced sinters, with corrosion rates of 0.091, 0.073 and 0.127 mm per year, respectively. It leaves no doubt that the good resistance of materials synthesized by powder metallurgy is due to the proper selection of the manufacturing process parameters, ensuring a high degree of material consolidation. This was further confirmed by the examinations of microstructure (optical microscopy and scanning electron microscopy) and the results of density tests (hydrostatic method). It has been shown that the obtained sinters were characterized by a compact, homogeneous and pore-free structure, though at the same time differentiated and multi-phase, while the densities of individual alloys reached a level close to the theoretical values. The Vickers hardness of the alloys was 334, 399 and 486 HV10, respectively.