The bimetallic welds are frequently utilized for pipeline transport system of the nuclear power plants. The occurrences of welding defects generally depend on the filler electrode as well as the electrode coatings during shielded metal arc welding process. This study involves the design of austenitic stainless steel welding electrodes for SS304L–SA516 bimetallic welds. The objective of research work includes the novel design of Al2O3–TiO2–CaO–SiO2 coatings by combining two ternary phase systems using extreme vertices mixture design methodology to analyze the effect of key coating constituents on the weld metal chemistry and mechanical properties of the welds. The significant effect of electrode coating constituent CaO on weld metal manganese content is observed which further improves the toughness of bimetallic weld joints. Various regression models have been developed for the weld responses and multi objective optimisation approach using composite desirability function has been adopted for identifying the optimized set of electrode coating compositions. The role of delta ferrite content in promoting the favourable solidification mode has been studied through microstructural examination. © IMechE 2021.