Photocatalysis offers an intriguing route for selective oxidation of CH4 to CH3OH under mild conditions. However, owing to the ultra-high stability of CH4 and the diversity of oxidative products, the activity of CH4 oxidation and the selectivity of CH3OH are still far from satisfactory. Herein, we report a dual-cocatalyst of Au and bimetallic oxide (Zn2Ti3O8) nanoparticles (NPs) modified TiO2 nanotube (Au/Zn2Ti3O8/TiO2) for highly active and selective photocatalytic oxidation of CH4 to CH3OH with O2 at room temperature. The introduction of Zn2Ti3O8 NPs is skillfully exploited the epitaxies of ZIF-8 on the surface of protonated titanate nanotubes (H-TNTs) and the followed thermal treatment with air. During photocatalytic CH4 oxidation, 1.7 %Au/Zn2Ti3O8/TiO2-4 achieved a formation rate of liquid oxygenates of 1200 μmol·gcat.–1·h−1 with a CH3OH selectivity of 91.5 %, which were much higher than those over 1.7 %Au/TiO2 and 1.7 %Au/ZnO. Mechanism investigation confirmed the presence of the strong electron interaction between Au NPs, Zn2Ti3O8 NPs and TiO2 nanotubes in 1.7 %Au/Zn2Ti3O8/TiO2-4, which intensified the charge polarization between Zn sites and Ti sites. These charge-polarized Zn-Ti sites were not only beneficial to the adsorption and activation of CH4, but also accelerated the further transformation of CH3OOH to CH3OH, as well as inhibited the excessive oxidation of CH3OH.