A novel Bi2W1−xMoxO6/Montmorillonite (MMT) nanocomposite was prepared by one-pot hydrothermal method. XRD, TEM, Raman, UV–vis, FT-IR, PL and XPS were employed to characterize the nanocomposites. The photocatalytic desulfurization properties of Bi2W1−xMoxO6/MMT nanocomposites were performed by oxidizing dibenzothiophene (DBT) in the model oil under visible light irradiation. Results indicate that the molar fraction of Mo doping has critical impact on the desulfurization rate. Adequate Mo doping may form well-defined “solid solution/co-precipitation” heterostructure of Bi2W1−xMoxO6/Bi2MoO6, which enhances the visible light absorption efficiency and promotes the separation rate of photogenerated electron-hole pairs, thus leads to the improved photocatalytic desulfurization performance. The desulfurization rate of the model oil can reach 95% when the molar fraction x is 0.7 under visible light irradiation for 3 h. •Novel Bi2W1−xMoxO6/montmorillonite nanocomposites were fabricated.•Montmorillonite benefited the adsorption of dibenzothiophene and immobilization of Bi2W1−xMoxO6 nanosheet.•Coherent Bi2W1−xMoxO6/Bi2MoO6 heterostructure facilitated the separation of photogenerated electron-hole pairs.•Molar fraction of Mo influenced the photocatalytic oxidation desulfurization.