The 9% Cr steels were developed for ultra-supercritical (USC) power plants to meet the requirements of high operating temperature and pressure. These steels are produced to operate at high temperatures where impact toughness is not a concern; however, it becomes important for the welded joints to have good impact toughness at room temperature for manufacturing. The present work investigates the effect of the post-weld heat treatment (PWHT) parameters, i.e., temperature and time, on the impact toughness of multi-pass gas tungsten arc welded (GTAW) joints of ferritic/martensitic grade P92 steel. The microstructural evolution in welded joints given varying post-weld temperatures and times was studied. The lath martensitic structure of the weld metal for the as-welded joints resulted in high hardness and low impact toughness. The weld fusion zone toughness was 12 J, which was lower than the minimum specified values of 41 J (ASME standards) and 47 J (EN ISO 3580:2017). The PWHT temperature and time were found to have a significant effect on the impact toughness of the weld metal. A drastic increase in the impact toughness of the weld metal was noticed, which was attributed to lath break-up, reduction in dislocation density and reduction in solid solution hardening. The maximum impact toughness of 124 J was measured for PWHT temperature and time of 760 °C and 120 min, respectively. The effect of PWHT parameters on tensile strength was also investigated, and test results showed that the joint was safe for USC boiler application as it failed from the region of the P92 base metal. The variation in microstructural evolution along the weldments resulted in hardness variation. PWHT led to homogeneity in microstructure and, ultimately, reduction in hardness value. According to the study, the optimum temperature and time for PWHT of a GTAW joint of P92 steel were found to be 760 °C and 120 min, respectively.