Three 9 wt% Cr ferrite/martensite steels (two alloyed with Si) have been exposed to oxygen-controlled LBE at 550 and 600 °C, respectively. The passivating oxide scale consists of a spinel layer plus internal oxidation zone (IOZ). By adding Si, the thickness of spinel layer is decreased while the IOZ is enhanced. Moreover, a Si-rich oxide layer is observed underneath the spinel layer on Si-containing samples after 2000 h exposure at 600 °C. Besides, the less visible cracks/exfoliations on Si-containing samples indicate the positive role of Si addition on scale adherence.