This paper addressed the issues of both direct and indirect synthesis of Ni aluminides by pack cementation (pure Ni and IN 718 superalloy). On the Al-Ni diffusion twosome under pressure, at temperatures below and above the Al melting temperature, the appearance and evolution of diffusion porosity because of the Kirkendall–Frenkel effect manifestation was highlighted. It has been confirmed that, as the temperature rises above the Al melting temperature, the porosity decreases. Nickel-based superalloys, and in particular IN 718, significantly increase their performance by increasing the aluminides proportion in the top diffusion coating. This is made possible by changing the value of the Al and Ni weight percentage ratio in this area (noted as Al/Ni). In the case of the diffusion twosome between IN 718 and pack aluminizing mixtures, having in their composition as active components Al powder, Ferroaluminum (FeAl40) or mixtures of Al and Fe powders, at processing temperatures above the Al melting temperature, by modifying the active component of the mixture, substantial changes in the Al/Ni values were observed, as well as in the maximum %Al in the diffusion coating and of its thickness. It was found that, when switching from Al to FeAl40 or powder mixture (Al + Fe), the Al/Ni value changes between 3.43 and 1.01, from initial subunit values. The experiments confirmed that the highest %Al in the top aluminized diffusion coating, for IN 718, was obtained if the powder mixture contained 66.34 wt.% Al.