AbstractCO2, a major contributor to global warming, can be balanced by converting it into fuels. The reduction of CO2 has been difficult due to its extremely high stability. Recently, single‐electron reduction of CO2 by superalkalis has been proposed using quantum chemical methods. Herein, we report a systematic study on the single‐reduction of CO2 by using typical superalkalis. Superalkalis are hypervalent species possessing lower ionization energies than alkali atoms. We have studied the interaction of CO2 with FLi2, OLi3, and NLi4 superalkalis using ab initio MP2 calculations. We notice that this interaction leads to stable superalkali‐CO2 complexes in which the structure of CO2 is bent due to electron transfer from superalkalis. This clearly reveals that the CO2 can successfully be reduced to the anion. It has been also noticed that the size of superalkalis plays a crucial in the single‐electron reduction of CO2. For instance, the binding energy of superalkali‐CO2 complex and charge transfer to CO2 decreases monotonically with the increase in the size of superalkali. We have also proposed that CO2 can be further reduced to in case of the anionic complex such as (FLi2CO2)‾. Thus, FLi2 superalkali is also capable of double‐electron reduction of CO2. These findings should provide new insights into CO2‐activation as well as motivate further research in this direction.