In-house prepared lithium carbonate doped CaO was tested for its CO2 sorption properties and suitability as a CO2 sorbent for sorption-enhanced reforming of methane. The new material demonstrated CO2 capacity at the temperatures above the equilibrium for CaO recarbonation reaction. However, the capacity was unstable and decreased during carbonation-regeneration cycles. After sufficiently large number of cycles Li dopant escaped from the sorbent and its sorption behavior resembled to that of CaO. The main route of escape is, probably, a crossover of liquid Li2CO3 onto crucible in TG experiments and onto catalyst in SER tests. Sorption enhanced methane reforming at 2 bar pressure, 750 degrees C and H2O to CH4 ratio of 4 using novel sorbent yielded as high as 99.8 vol% pure hydrogen during the first cycle. In subsequent cycles the hydrogen purity drastically decreased as a result of severe catalyst poisoning by Li. (C) 2011 Elsevier Ltd. All rights reserved.