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The photocatalytic activity of TiO₂ depends on numerous factors, such as the chemical potential of electrons, charge transport properties, band-gap energy, and concentration of surface-active sites. A lot of research has been dedicated to determining the properties that have the most significant influence on the photocatalytic activity of semiconductors. Here, we demonstrated that the activity of TiO₂ in the gas-phase reduction of CO₂ is governed mainly by the desorption rate of the reaction intermediates and final products. This indicates that the specific surface area of TiO₂ and binding strength of reaction intermediates and products are the main factors affecting the photocatalytic activity of TiO₂ in the investigated process. Additionally, it was shown that rutile exhibits higher photocatalytic activity than anatase/rutile mixtures mainly due to its high efficiency in the visible portion of the electromagnetic spectrum.