Porous sulfur-doped titanate was synthesized by hydrothermal method as the support of amine for CO2 capture. Tetraethylenepentamine (TEPA) was selected as the modifier to enhance CO2 adsorption capacity and selectivity by the introduction of chemisorptions. The physicochemical properties of raw and TEPA modified sulfur-doped titanate were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (IR), as well as low temperature N2 adsorption. CO2 adsorption and desorption were investigated by a fixed bed reactor system and temperature programmed desorption (TPD), respectively. With the maximum TEPA loading of 45wt%, the maximum CO2 adsorption capacity reached 3.58mmol/g at 70°C. The adsorption capacity for CO2 remained almost the same after cyclic regeneration experiments. Ultimately, the results of characterization and experiments were summarized to understand the CO2 adsorption–desorption mechanism.