Abstract Hybrid systems dedicated to waste transmutation are constituted of an accelerator generating a high energy proton flux, a spallation target on which the accelerated proton beam impinges to produce neutrons and a subcritical core. The Pb–Bi eutectic liquid alloy is considered as spallation target material due to its suitable nuclear and physical properties. However, liquid metals can be corrosive towards containment materials (austenitic and Fe9Cr alloys). In the case of liquid lead bismuth alloy, one of the protection means considered against the dissolution of the steels is the in situ protection by the formation of an oxide layer at the steels’ surface. However, in order to ensure the efficient protection of the steels by an oxide layer, the control and the monitoring of the oxygen content in the Pb–Bi alloy is a major issue. The paper recalls, first, the oxygen chemistry in a lead alloy system, in order to propose the oxygen operating window that complies with both the contamination by lead oxide of the coolant and the corrosion control by the promotion of an oxide film on the structure. Results of tests performed in stagnant lead bismuth at high oxygen concentrations are also presented showing the effect of various operating parameters on the oxidation kinetics and on the nature of the oxide layer. An oxidation mechanism and model are also proposed and compared with experimental data.