The ZnO nanoparticles are prepared by a precipitation process, and also are char- acterized by means of the modern testing techniques such as XPS, ESR, SPS and PL. The ac- tivity of the as-prepared ZnO is evaluated in the photocatalytic oxidation of gas phase n-C7H16. The relationships of surface oxygen vacancies (SOV) with photoluminescence (PL) and photo- catalytic performance are discussed in details. The results show that the smaller the particle size, the larger the SOV content, the stronger the PL signal, the higher the photocatalytic activity, in- dicating that the SOV, PL and photocatalytic activity have inherent relationships. This was be- cause of the reasons that the PL signal is attributed to the free and binding excitons resulting from the SOV, while the SOV is favorable for a photocatalytic oxidation reaction since the SOV can easily capture the photoinduced electrons, and the captured electrons had strong interac- tions with the adsorbed oxygen. In addition, the surface states of ZnO nanoparticles, arising from the SOV and oxygen species, are very abundant. The ZnO nanoparticles are prepared by a precipitation process, and also are char-acterized by means of the modern testing techniques such as XPS, ESR, SPS and PL. The ac- tivity of the as-prepared ZnO is evaluated in the photocatalytic oxidation of The relationships of surface oxygen vacancies (SOV) with photoluminescence (PL) and photo-catalytic performance are discussed in details. The results show that the smaller the particle size, the larger the SOV content, the stronger the PL signal, the higher the photocatalytic activity, in- dicating that the SOV, PL and photocatalytic activity have inherent relationships. the was that the PL signal is attributed to the free and binding excitons resulting from the SOV, while the SOV is favorable for a photocatalytic oxidation reaction since the SOV can easily capture the photoinduced electrons, and the fenced electrons have a strong interactivity with the adsorbed oxygen. e surface states of ZnO nanoparticles, arising from the SOV and oxygen species, are very abundant.