To remove tar and produce environment-friendly H2, one of the promising routes is the sorption-enhanced steam reforming (SESR) process, in which the CO2 sorbent is a key element. We prepared the CO2 sorbents with Ca12Al14O33 as carrier with various methods. Their characterizations were examined, and the sample prepared by solgel (SG) method showed the strongest CaO and Ca12Al14O33 phases and the most excellent pore structure among all the samples. Then, a thermogravimetric experiment was conducted, and the results showed that the sample prepared by sol-gel (SG) method had the best CO2 adsorption capacity and excellent long-term cyclic stability. Finally, the sorbent was used into the steam reforming experiments of tar. Under the action of the sorbent, the reforming reaction was enhanced in-situ, with the H2 yield and concentration improved obviously, and especially, H2 concentration can reach over 98.85%.