In this study, two grades of Aluminium–Lithium alloys: AA8090 and AA2050 have been selected. Butt joints were produced using the Rotating arc welding process (SpinArc™) with ER4043 filler. Two different groove joints, Square Butt and V-Groove, were used during the process. The joints were subjected to analysis of microstructure, mechanical properties and electronic work function. A correlation was brought out between all these tests. The microstructure analysis showed the formation of Mg2Si and Al2Cu eutectics. It was also found that the joint made using the Square Butt joint exhibited greater weld strength and enhanced work function. Electron microscopy and XRD analysis revealed the presence of different strengthening precipitates at various zones.