Highly efficient NaF-doped Li4SiO4 sorbents were synthesized by sacrificial carbon template technology to overcome their typical kinetic limitations at low CO2 concentrations. The samples were characterized by XRD, SEM, N2 adsorption, XPS, differential scanning calorimetry (DSC), and thermogravimetric analyses (dynamic and isothermic). The results showed that co-doped sodium and fluorine were substituted for lithium and oxygen, respectively. Such doped features induced a high concentration of Li-O sites on the molten surface when absorbing CO2 in a relatively wide temperature range (475–575°C). This favorable characteristic greatly facilitated surface chemisorption processes, accelerated the transport of Li+ and O2−, and decreased the CO2 diffusion resistance. Therefore, 3wt.% NaF doping was used to reach a maximum absorption capacity (>33.0wt.%) in a wide temperature range (475–575°C) in 15vol.% CO2. Moreover, the high capacity was maintained over 10 sorption/desorption cycles, suggesting that NaF-doped Li4SiO4 sorbents have high potential for CO2 capture.