The manuscript described the effect of Ni-based filler on microstructure and mechanical properties of the dissimilar welded ASTM A335 grade P22 and P91 alloy steel plate. The dissimilar welds joint (DWJ) was produced using the Gas Tungsten Arc Welding (GTAW) process. The DWJ was characterized for metallographic and mechanical testing for as-welded and post-weld heat treatment (PWHT) conditions. For mechanical properties, microhardness, tensile test and Charpy impact test were performed. The DWJ showed the heterogeneity in microstructure and mechanical properties (microhardness, impact toughness) along the welded joint. The weld metal showed the formation of the austenitic microstructure consisted of the equiaxed dendrite along with segregation of the alloying elements like Cr, Mo, and Ti at the inter-dendritic boundaries, while P91 and P22 HAZ showed the formation of coarse-grained, fine-grained, and inter-critical heat-affected region depends on the temperature experienced during the welding cycle. The region of P91 HAZ was characterized by untempered and tempered martensite, while P22 HAZ was characterized by coarse and fine bainitic microstructure. The PWHT showed a negligible effect on the microstructure of the weld metal, while a significant change in microstructure of P91 HAZ and P22 HAZ was observed. PWHT also led to the formation of the soft and hard zone along the interface of the P22 steel due to the carbon diffusion. At the interface of the weld metal and base material, a sharp gradient was observed for the elements Cr, Fe, Ni and Mo. The weld metal near the interface showed the columnar dendritic structure having segregation of the alloying elements Mo, Ti and Cr along the inter-dendrite boundaries. A variation in hardness was measured along the weldments for as-welded and PWHT conditions. The peak hardness was measured in P91 coarse-grained heat-affected zone (CGHAZ) for both as-welded and PWHT, while the poor hardness of 202 HV and 195 HV was measured for weld metal in as-welded and PWHT conditions. The strength of the welded joint was measured higher than the strength of P22 steel for both conditions; however, the fracture was observed in P22 base metal for the as-welded joint, while in PWHT, it was in P22 HAZ near the interface. A variation in Charpy impact toughness was observed along the weldment for both as-welded and PWHT conditions. In as-welded, the minimum Charpy impact toughness (CIT) of 95.8 J was measured in weld metal, while the maximum was 152 J in P91 HAZ. After the PWHT HAZ region of P22 and P91 steel showed a drastic increase in CIT, however reduction in CIT of the weld metal was measured. © 2021 Elsevier Ltd