Material compatibility is a major challenge in the development of liquid metal batteries. In this study, the corrosion behavior of two candidate positive current collector materials, austenitic stainless steel and molybdenum, in Na//SbBi9 liquid metal batteries is investigated. In-situ corrosion in operating cells is compared with static corrosion in SbBi9 (corresponding to the fully charged state) and Na0.30Sb0.07Bi0.63 (representing the fully discharged state) at 450 °C. Stainless steel shows a much better corrosion resistance in Na-Sb-Bi alloy (corrosion depth below 1 μm after 750 h static exposure) than in SbBi9 (7–9 μm corrosion layer) thanks to the formation of a thin oxide layer. The corrosion under cycling conditions shows similar characteristics (formation of solid Fe-Cr-Ni-Sb compounds), though accelerated, as static exposure to SbBi9. Molybdenum exhibits a very good corrosion resistance both in static and in cycling conditions, showing merely a minor dissolution into the adjacent alloy.