High-purity hydrogen is usually produced through increasing inventory of CO2 sorbents in the sorption enhanced steam reforming (SESR) processes. Herein, we report an effective approach to the high-purity hydrogen from SESR of glycerol by modifying a bi-functional Co-CaO catalyst to suppress the methanation side-reaction, which significantly consumes hydrogen. Bimetallic Co-based catalysts containing Ni, Cu and Zn were prepared from hydrotalcite-like materials as precursors. Over the 10Co-5Cu catalyst, the highest hydrogen purity up to 99.27% could be reached. Through temperature programmed desorption, oxidation, hydrogenation and CO disproportionation reactions, it was revealed that copper suppressed the formation of active coke species and CO methanation, thus alleviated the hydrogen consumption to allow for the production of high-purity hydrogen through SESR of glycerol. (C) 2017 Elsevier B.V. All rights reserved.