Photocatalytic activity and lifetime of photoexcited carriers on well-defined single-crystalline anatase and rutile TiO2 surfaces with different surface orientation have been systematically studied by photoelectron spectroscopy. Photocatalytic activity, evaluated with reference to the photocatalytic degradation of acetic acid, has a positive and linear correlation with carrier lifetime at the crystal surface, which was determined by following the time evolution of the ultraviolet-induced surface photovoltage. This indicates that the carrier lifetime is a prime factor for the photocatalytic activity so that it can be viewed as the origin of the crystal-surface-orientation dependence of the photocatalytic activity.