Creating hardening coatings through thermo-reactive diffusion is an effective method for increasing the service life of cast iron parts. The influence of aluminium on the process of thermo-reactive diffusion of cast irons with vanadium has been studied. It has been found that the concentration of aluminium in the reaction powder medium affects the structure, thickness, and hardness of the coating. The most optimal concentration of aluminium is 0.5–2.5%. This concentration makes it possible to increase the thickness of the hardened coating by 1.5 times with a decrease in microhardness by 10–25% compared to pure vanadization.