Integrated CO2 capture and conversion (ICCC) using dual-function materials (DFMs) is one of the key technologies for addressing critical global environmental and energy issues. DFMs generally consist of alkali or alkaline earth metals for CO2 capture and transition metal catalysts for CO2 conversion. In this study, we studied the ICCC to CO using transition-metal-free DFMs to demonstrate their potential to directly produce syngas from atmospheric-level CO2. Among the DFMs prepared herein, Na/Al2O3 exhibited excellent performance and achieved a CO2 conversion exceeding 90% and CO selectivity exceeding 95% at a reaction temperature of 450-500 °C. Na/Al2O3 maintained its capture and conversion capacity throughout a 50-cycle stability test without significant deactivation. Furthermore, in the scale-up experiments using Na/Al2O3 DFM, a syngas-like mixture an H2/CO molar ratio of 3.3 (48.1 vol% H2 and 14.5 vol% CO) was directly obtained from 400 ppm CO2. These results suggest that ICCC using the transition-metal-free Na/Al2O3 DFM may be practicable provided the CO2 capture capacity of the DFM is further improved while maintaining the aforementioned advantages.