This study reports the effect of 650 °C exposure on microstructural evolution and creep behavior of post-weld heat-treated dissimilar welds between the alloys T92 and Super304H. The dissimilar welds were exposed for durations of 24 h, 100 h, 250 h, 500 h, and 1000 h to investigate the thermal stability of the microstructure. Creep tests were carried out at 650 °C and 120 MPa on the post-weld heat-treated and on 1000 h exposed dissimilar metal welds. The isothermal exposure degraded the microstructure of T92-HAZ, resulting in type IV failure at an accelerated rate under creep conditions. Further, accelerated recovery of martensitic laths and extensive precipitation of Laves phase on M₂₃C₆ carbides sitting at the grain boundaries of the fine-grained heat-affected zone (FGHAZ) during creep deformation were observed. The isothermal exposure on Super304H-HAZ showed no significant microstructural changes except precipitation of thick M₂₃C₆ carbides at the grain boundaries. These prominent microstructural changes in the HAZ of T92 lead to the accelerated void formation in the FGHAZ and are responsible for consequent premature failure.