Adsorption of CO 2 on a semiconductor surface is a prerequisite for its photocatalytic reduction. Owing to superior photocorrosion resistance, nontoxicity, and suitable band-edge positions, TiO 2 is considered to be the most efficient photocatalyst for facilitating redox reactions. However, due to the absence of adequate understanding of the mechanism of adsorption, the CO 2 conversion efficiency on TiO 2 surfaces has not been maximized. While anatase TiO 2 (101) is the most stable facet, the (001) surface is more reactive, and it has been experimentally shown that the stability can be reversed and a larger percentage (up to ∼89%) of the (001) facet can be synthesized in the presence fluorine ions. Therefore, through density functional calculations we have investigated the CO 2 adsorption on TiO 2 (001) surfaces. We have developed a three-state quantum-mechanical model that explains the mechanism of chemisorption, leading to the formation of a tridentate carbonate complex. The electronic structure analysis reveals that the CO 2 -TiO 2 interaction at the surface is uniaxial and long ranged, which gives rise to anisotropy in binding energy (BE). It negates the widely perceived one-to-one correspondence between coverage and BE and infers that the spatial distribution of CO 2 primarily determines the BE. A conceptual experiment is devised where the CO 2 concentration and flow direction can be controlled to tune the BE within a large window of ∼1.5eV. The experiment also reveals that a maximum of 50% coverage can be achieved for chemisorption. In the presence of water, the activated carbonate complex forms a bicarbonate complex by overcoming a potential barrier of ∼0.9eV. © 2018 American Physical Society.