The Venturi-type solid-phase oxygen control system with a bypass mass exchanger is widely regarded as an effective approach to keep the oxygen concentration in the LBE under reasonable ranges to reduce the corrosion. In this work, numerical simulations of the particle–fluid mass transfer of the oxygen concentration in LBE are performed for the 1:1 scale 3D UPBEAT loop under various conditions. The discrete element method is applied to generate the geometry of the packing of the PbO spheres. The velocity profile and oxygen concentration governing equations are solved by using the SST turbulence model. At the same temperature, the oxygen mass transfer coefficient increases monotonically with the flow rate. At the same mass flow rate, the mass transfer coefficient increases with the temperature, reaching a maximum at about 475 °C. It provides guidance for future research in the design and optimization of oxygen control systems under high temperature in lead–bismuth nuclear reactors.