This study explored 6061 Al alloy and AZ31B Mg alloy joined by TIG lap welding with Zn foils of varying thicknesses, with the additional Zn element being imported into the fusion zone to alloy the weld seam. The microstructures and chemical composition in the fusion zone near the Mg substrate were examined by SEM and EDS, and tensile shear strength tests were conducted to investigate the mechanical properties of the Al/Mg joints, as well as the fracture surfaces, and phase compositions. The results revealed that the introduction of an appropriate amount of Zn transition layer improves the microstructure of Mg/Al joints and effectively reduces the formation of Mg-Al intermetallic compounds (IMCs). The most common IMCs in the fusion zone near the Mg substrate were Mg-Zn and Mg-Al-Zn IMCs. The type and distribution of IMCs generated in the weld zone differed according to Zn additions; Zn interlayer thickness of 0.4 mm improved the sample’s mechanical properties considerably compared to thicknesses of less than 0.4 mm; however, any further increase in Zn interlayer thickness of above 0.4 mm caused mechanical properties to deteriorate.