The effect of the post-weld heat treatment on the microstructures and mechanical properties of the dissimilar joint of G115, a novel developed martensite heat resistant steel, and CB2 steel, currently used in an ultra-super-critical power unit, was investigated. The results indicate that the quenched martensite underwent decomposition and transformation, and the amount of dislocations were sharply decreased in the weld metal after post-weld heat treatment (PWHT). Many nano-scale M₂₃C₆ precipitates present in the weldment were distributed on the grain and grain boundary in a dispersed manner with PWHT. The average microhardness of the weldment decreased from about 400 HV to 265–290 HV after PWHT and only a slight decrease in the microhardness of CB2 steel was detected after PWHT at 760 °C. In contrast to the case of the as-received joint, the tensile strength of the joint was improved from 630 MPa to 694 MPa and the fracture location moved from the weld metal to the base metal after PWHT. The fracture surface consisted of a cleavage fracture mode without PWHT, whereas many dimples were observed on the fracture surface with PWHT.