In this paper, TiO2 nanoparticles doped with different amounts of Zn were prepared by a sol-gel method and were mainly characterized by means of X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and surface photovoltage spectrum (SPS). The effects of surface oxygen vacancies (SOVs) of Zn-doped TiO2 nanoparticles on photophysical and photocatalytic processes were investigated along with their inherent relationships. The results show that the SOVs easily bind photoinduced electrons to further give rise to PL signals. The SOVs can result in an interesting sub-band SPS response near the band edge in the TiO2 sample consisting of much anatase and little rutile, except for an obvious band-to-band SPS response. Moreover, the intensities of PL and SPS signals of TiO2, as well as the photocatalytic activity for degrading phenol solution, can be enhanced by doping an appropriate amount of Zn. These improvements are mainly attributed to the increase in the SOV amount. It can be suggested that the SOVs should play an important role during the processes of PL, surface photovoltage, and photocatalytic reactions, and, for the as-prepared TiO2 samples doped with different amounts of Zn by thermal treatment at 550℃, the larger the SOV amount, the stronger the PL and SPS signal, and the higher the photocatalytic activity.