During the die-casting process as well as the hot forming process, the tool is subjected to complex thermal, mechanical, and chemical stresses that can cause various types of damage to different parts of the tool. This study was carried out to determine the resistance of various tool steels, i.e., UTOPMO1, HTCS-130, and W600, in molten Al99.7 aluminum alloy at a temperature of 700 °C. The formation kinetics of the interaction layer between the molten aluminum and tool steels was studied using differential scanning calorimetry. Light and field-emission scanning electron microscopy were used to analyze the thickness and nature of the interaction layers, while thermodynamic calculations using the Thermo-Calc software were used to explain the results. The stability of the HTCS-130 and W600 tool steels is better than the stability of the UTOPMO1 tool steel in the molten Al99.7 aluminum. Two interaction layers were formed, which in all cases indicate an intermetallic Al Fe layer near the aluminum alloy and an intermetallic Al Fe layer near the tool steels, containing small round carbides. It was confirmed that Ni reduces the activity of aluminum in the ferrite matrix and causes a reduction in the thickness of the intermetallic layer.