The dissimilar combinations of Inconel 625 and duplex stainless steel SAF 2205 obtained from manual GTA welding process employing ER2209 and ERNiCrMo-3 filler metals have been investigated. Formation of secondary phases at the HAZ of Inconel 625 and grain coarsening at the HAZ of SAF 2205 were witnessed while using these filler wires. The average hardness of ER2209 weldments was found to be greater than ERNiCrMo-3 weld. Tensile fracture was observed at the weld zones for both the fillers. Impact test trials showed brittle mode of fracture on employing ER2209 filler and mixed (ductile-brittle) mode of fracture while using ERNiCrMo-3 filler. Further optical microscopy and SEM/EDS analysis were carried out across the weldments to investigate the structure-property relationships. © The Chinese Society for Metals and Springer-Verlag Berlin Heidelberg 2014.