Developing photocatalysts with high efficiency and selectivity for CO2reduction is essential in the sight of both energy and environment. Through comprehensive density functional theory calculations, we have found that B80fullerene can be used as an excellent metal-free photocatalyst for reducing CO2to value-added chemicals in this report. Our results reveal that electron-deficient boron fullerene can effectively activate CO2(Lewis acid) through Lewis acid–base interactions on the three basic sites of B80(B80is an amphoteric molecule). The charge density difference analysis indicates that there are significant charge transfers between CO2and B80fullerene on the adsorption sites, which are responsible for the activations of CO2. On the basis of calculating the adsorption energies of the possible products (CO, HCOOH, CH2O, CH3OH, and CH4) on B80fullerene and the possible reaction pathways producing these products, the B80fullerene shows high efficiency and selectivity for producing HCOOH. The minimum |Ulim| (0.18 V) of the reaction pathway to produce HCOOH and weaker binding of HCOOH on B80fullerene (the adsorption energy is −0.51 eV) than the counterparts of CO2both indicate that the formation and release of HCOOH from the B80fullerene surface is feasible. In all, our work provides useful information for searching for an excellent metal-free photocatalyst for CO2reduction.