The main drawback of friction stir welding (FSW) dissimilar metals is the formation of intermetallic compounds (IMCs), which are brittle and affect the strength of the joint. The formation of these compounds is inevitable due to their low enthalpy of formation; however, their emergence is an indication of metallurgical bonding between dissimilar metals. This means that the determining factors of intermetallics should be optimal to ensure the formation of the joint and, at the same time, the performance of the joint. It is known that various parameters such as welding parameters, joint configuration, and tool geometry have an influence on the formation of these compounds. However, the influence of the base metal is not adequately addressed in the literature. The current review paper focuses on intermetallic formation during the friction stir welding of aluminum/steel (Al/St) alloys to explore how the types of alloys affect the thicknesses and morphologies of the intermetallics. Different structural steels and stainless steels were considered to see how they affect intermetallic formation when welded to different types of aluminum alloys. The thicknesses of the IMCs in the FSW of different aluminum/steel alloys were taken from the literature and averaged to provide insight into the contribution of the elements to IMC formation. Thermodynamic and kinetic analyses were used to explain this effect. Finally, the mechanism of intermetallic formation is explained to provide a useful guide for selecting dissimilar metals for welding using friction stir welding.