Nickel-aluminum alloys are widely used in harsh environments due to their corrosion resistance, high melting temperature, and thermal conductivity. In this work, Ni-5wt%Al coatings were deposited by twin-wire arc spraying (TWAS) on tool steel using a design of experiments approach to study the effect of process parameters on coating microstructure and performance. Test results presented in the form of process maps show how N2 pressure, stand-off distance, and current affect in-flight particle velocity and temperature as well as coating thickness and oxide content. Using this information, optimized coatings were then deposited on test substrates and subjected, along with uncoated tool steel, to several hours of molten aluminum attack. The coated samples showed no signs of physical or chemical damage, whereas the uncoated substrates experienced oxidation, aluminum infiltration, and formation of Fe-Al intermetallics.