Understanding trends in the formation of the intermetallic compound (IMC) layer in Al/Fe bimetallic composites can aid in significantly improving their mechanical properties. However, it is currently challenging to predict IMC layer formation during hot-dip aluminizing. Furthermore, the results from previous studies are difficult to compare owing to the variation in the process parameters used. Therefore, to understand how temperatures and holding times affect the thickness and hardness properties of IMC layers, we investigated the interfacial properties of aluminized stainless steel in molten Al-Si-Mg. AISI 420 stainless steel was hot-dip aluminized in an Al–Si–Mg alloy melt for 10–120 min at four different temperatures: 700, 750, 800, and 850 °C. Morphology, type, and element distribution of the phases formed in the reaction layer and the reduction rate of the aluminizing process were studied. Notably, while the reaction layer thickness increased with increasing aluminizing temperature when the holding time was low, long-term reaction caused the reaction layer to become thicker at lower temperatures. The mechanism of this morphological transformation is discussed. The results demonstrated effective trends in controlling the morphology of the intermetallic compound layer with respect to various hot-dip Al plating process parameters.