The microstructure and mechanical properties of NiCrMoV-and NiCrSi-alloyed medium-carbon steels were investigated after multiple tempering. After austenitising, the steels were hardened by oil quenching and subsequently double or triple tempered at temperatures from 250 to 500 °C. The samples were characterised using scanning electron microscopy and X-ray diffraction, while the mechanical properties were evaluated by Vickers hardness testing, V-notched Charpy impact testing and tensile testing. The results showed that the retained austenite was stable up to 400 °C and the applied multiple tempering below this temperature did not lead to a complete decomposition of retained austenite in both steels. It was also found that the microstructure, hardness and impact toughness varied mainly as a function of tempering temperature, regardless of the number of tempering stages. Moreover, the impact toughness of NiCrMoV steel was rather similar after single/triple tempering at different temperatures, while NiCrSi steel exhibited tempered martensite embrittlement after single/double tempering at 400 °C. The observed difference was mainly attributed to the effect of precipitation behaviour due to the effect of alloying additions in the studied steels.