The effect of tempering after water quenching on the strength and fracture toughness of two steels with chemical compositions of 0.34%C-1.77%Si-1.35Mn-0.56%Cr-0.2%Mo-0.04%Nb-0.03Ti-0.002B and 0.44%C-1.81%Si-1.33%Mn-0.82%Cr-0.28%Mo was examined. The last steel exhibits quenching embrittlement in an as-quenched condition. At a tempering temperature of 280 °C, the precipitation of transition η–Fe2C carbides in martensitic matrix leads to increasing fracture toughness and eliminates quench embrittlement in the steel with 0.44 wt.%C. Tempered martensite embrittlement at 400 °C appears as decreased values of the Charpy V-notch impact energy, ductility and the product of strength and elongation, σB´δ (MPa´%) and is attributed to increased effective grain size for fracture, mainly. The precipitation of boundary cementite takes place at tempering at 500 °C and provides increased ductility and fracture toughness despite a decohesion along carbide/ferrite interfaces. The low severity of TME in Si-rich low-alloy medium carbon steels is attributed to the suppression of boundary cementite precipitation at tempering temperatures ≤400 °C.