Transition joints between ferritic steel and austenitic stainless steel are commonly encountered in high-temperature components of power plants. Service failures in these are known to occur as a result, mainly, of thermal stresses due to expansion coefficient differentials. In order to mitigate the problem, a trimetallic configuration involving an intermediate piece of a material such as Alloy 800 between the ferritic and austenitic steels has been suggested. In our work, modified 9Cr-1Mo steel and 316LN stainless steel are used as the ferritic and austenitic components and the thermal behavior of the joints between modified 9Cr-1Mo steel and Alloy 800 is described in this article. The joints, made using the nickel-base filler material INCONEL 82/182 (INCONEL 82 for the root pass by gas-tungsten arc welding and INCONEL 182 for the filler passes by shielded-metal arc welding), were aged at 625 °C for periods up to 5000 hours. The microstructural changes occuring in the weld metal as well as at the interfaces with the two parent materials are characterized in detail. Results of across-the-weld hardness surveys and cross-weld tension tests and weld metal Charpy impact tests are correlated with the structural changes observed. Principally, the results show that (1) the tendency for carbon to diffuse from the ferritic steel into the weld metal is much less pronounced than when 2.25Cr-1Mo steel is used as the ferritic part; and (2) intermetallic precipitation occurs in the weld metal for aging durations longer than 2000 hours, but the weld metal toughness still remains adequate in terms of the relevant specification.