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.