Aqueous solvated electron (eaq–), a key species in radiation and plasma chemistry, can efficiently reduce CO2 in a potential green chemistry application. Here, the mechanism of this reaction is unravelled by condensed-phase molecular dynamics based on the correlated wave function and an accurate density functional theory (DFT) approximation. Here, we design and apply the holistic protocol for solvated electron’s reactions encompassing all relevant reaction stages starting from diffusion. The carbon dioxide reduction proceeds via a cavity intermediate, which is separated from the product (CO2–) by an energy barrier due to the bending of CO2 and the corresponding solvent reorganization energy. The formation of the intermediate is caused by solvated electron’s diffusion, whereas the intermediate transformation to CO2– is triggered by hydrogen bond breaking in the second solvation shell of the solvated electron. This picture of an activation-controlled eaq– reaction is very different from both rapid barrierless electron transfer and proton-coupled electron transfer, where key transformations are caused by proton migration.