DUT-67(Zr) was obtained by a solvothermal route and applied to photocatalytic selective synthesis of thioanisole under light illuminating. The conversion of thioanisole is up to 95%, and the selectivity of methyl phenyl sulfoxide is 98%. The activity of DUT-67(Zr) is over 10 times higher than that of UiO-66. This great increased activity is attributed to the high percentages of oxygen vacancies on DUT-67(Zr). The ESR result shows there are more oxygen vacancies that can expose high density unsaturated Zr sites on DUT-67(Zr). The in situ FTIR reveals that unsaturated Zr sites on DUT-67(Zr) possess Lewis acidity which facilitate the adsorption of the substrates to form the coordination species, promoting the activation of thioanisole. The absorption edge of DUT-67(Zr) with coordination species red-shifts to 360 nm, which can be presented by DRS. Furthermore, the oxygen molecules can be activated by excited electrons to form •O2-. Finally, a possible photocatalytic process of oxidating thioanisole to methyl phenyl sulfoxide based on the coordination effect between DUT-67(Zr) and thioanisole is proposed at a molecular level.