A sodium chloride (NaCl) doping-hydration technique was used to modify the structure of Li4SiO4 to improve its sorption properties at a low CO2 concentration. X-ray diffraction, nitrogen adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, differential scanning calorimetry, and thermogravimetric analyses were conducted to characterize the compositions, textural characteristics, morphologies, chemical valenee states, molten phases, and adsorption properties of the synthesized samples. Hydration and NaCl doping produced synergistic effects. On one hand, a small particle size and large specific surface area were obtained, significantly facilitating chemisorption processes. On the Other hand, co-droped sodium and chlorine induced molten phases when absorbing CO2, noticeably decreasing CO2 diffusion resistance. Thus the CO2 absorption rate and uptake were remarkably improved. Different amounts of NaCl also greatly affected the morphology and chemisorption properties of the sorbents, At the optimized NaCl concentration, the sorbent only required 3 wt % doping to attain a Maximum sorption capacity of up to 34.2 wt %. Moreover, the high capacity was maintained after 10 sorption/desorption cycles.