Iron-based oxygen carriers (OCs) have received much attention due to their low costs, high mechanical strengths and high-temperature stabilities in the chemical looping gasification (CLG) of biomass, but their chemical reactivity is very ordinary. Converter steel slags (CSSs) are steelmaking wastes and rich in Fe2O3, CaO and MgO, which have good oxidative ability and good stability as well as catalytic effects on biomass gasification. Therefore, the composite OCs prepared by mechanically mixing CSSs with iron-based OCs are expected to be used to increase the hydrogen production in the CLG of biomass. In this study, the catalytic performance of CSS/Fe2O3 composite OCs prepared by mechanically mixing CSSs with iron-based OCs on the gasification of brewers’ spent grains (BSGs) were investigated in a tubular furnace experimental apparatus. The results showed that when the weight ratio of the CSSs in composite OCs was 0.5, the relative volume fraction of hydrogen reached the maximum value of 49.1%, the product gas yield was 0.85 Nm3/kg and the gasification efficiency was 64.05%. It could be found by X-ray diffraction patterns and scanning electron microscope characterizations that the addition of CSSs helped to form MgFe2O4, which are efficient catalysts for H2 production. Owing to the large and widely distributed surface pores of CSSs, mixing them with iron-based OCs was beneficial for catalytic steam reforming to produce hydrogen.