The objective of this study is to develop a new low-cost, highly selective, and stable sorbent based pre-combustion CO2 capture. A high surface area titanium oxide (TiO2) prepared by a template method and amine modified TiO2 (M-TiO2) were investigated for CO2/CH4 adsorption at conditions relevant to pre-combustion CO2 capture. Single-component and binary CO2/CH4 adsorption tests at different operating conditions were performed in a fixed bed adsorber. Experimental results show that the selectivity of TiO2 for separation of CO2 from CO2/CH4 mixture can be significantly improved via amine modification. The selectivity of CO2 over CH4 for M-TiO2 is enhanced to 22.1 at 333 K and 35 bar. Pure CO2 or CH4 can be obtained from the adsorber packed with M-TiO2 through cyclic CO2/CH4 mixture gas adsorption and desorption. The study indicates that, as a pre-combustion sorbent, the inexpensive mesoporous M-TiO2 is not only capable and stable, but also easily regenerated without loss of capacity and selectivity. (C) 2015 Elsevier Ltd. All rights reserved.