LAUSR

TiO2@UiO‐66 composite with intimate contact interfaces is fabricated by in situ solvothermal methods. Compared with other UiO‐based composites, TiO2@UiO‐66 exhibits superior photocatalytic activity for oxidation of toluene into CO2 during long‐time reaction under flowing conditions. This is because (1) the intimate contact interface and well‐matched band structure between TiO2 and UiO‐66 can effectively separate and transfer photogenerated electrons; (2) the synergistic effect between UiO‐66 and TiO2 promotes the adsorption of toluene and desorption of CO2 and provides sufficient active sites for photocatalytic reaction. The toluene conversion and CO2 production on 4TiO2@U are 3.27 and 4.10 times higher than that on UiO‐66, respectively. 4TiO2@U also shows the highest activity for formaldehyde and rhodamine B degradations. The in situ FTIR results exhibit that toluene can be oxidized by .O2− and h+ to benzaldehyde and benzoic acid, then further oxidized to oxalic acid, and finally mineralized into CO2 and H2O.