Abstract The high-temperature temper embrittlement of martensitic heat-resistant 10Cr12Ni steel was studied. The results demonstrate that there is some irreversible temper embrittlement when the steel is tempered at 625 °C. The irreversible temper embrittlement can be overcome by re-tempering at higher temperature. The tempered martensite embrittlement at 625 °C is attributed to the precipitation of M 23 C 6 -type carbides along the martensite lath and prior austenite grain boundaries. The tempering process can be divided into three stages: In the first stage, the martensite laths recover and M 7 C 3 -type carbides precipitate inside the martensite laths, leading to the improvement of the toughness. In the second stage, M 7 C 3 -type carbides dissolve, and M 23 C 6 -type carbides precipitate along the martensite laths and prior austenite grain boundaries. The M 23 C 6 -type carbides play a nucleating role in the development of cracks, leading to tempered martensite embrittlement. In the third stage, the toughness gradually recovers with the further recovery of the martensite laths.