This work examines the influence of post-weld heat treatment (PWHT) on the fusion zone microstructure, and mechanical properties of electron beam (EB)-welded alloy 686. Comparative studies have been made on weld microstructure and tensile properties of the weldments both in as-welded and post-welded heat-treated conditions. PWHT consists of direct aging (DA/480°C for 3 h) and solution treatment (ST, 980°C for 1 h) followed by ageing and finally, homogenizing treatment (HT, 1200°C for 1 h) followed by DA and ST. The secondary topologically closed packed (TCP) phases formation, their distribution and microsegregation characteristics are studied with the aid of scanning electron microscope (SEM) analysis. Energy-dispersive X-ray spectroscopy (EDS) is also performed to estimate the microsegregation of alloying elements in the dendritic core and interdendritic regions of the weldments. The result shows that there is no significant change in the microstructure of DA and solution-treated sample as compared to the as-welded sample. The microstructure of HT sample was entirely different from those of as-welded and other HT samples. The SEM/EDS analysis illustrates the presence of secondary TCP phases (r, P and l) in the as-weld, DA and ST condition, whereas HT weldments did not show the presence of TCP phases. Tensile test results show higher tensile strength in ST condition whereas homogenization samples show higher ductility compared with others.