The heterogeneous catalysts of Fe and Cu-doped monolacunary tungstosilicate have been prepared and characterized by SEM, XRD, IR, XPS, ICP, TG-DSC and H2-TPR techniques. The influence factors on the structure of catalysts and catalytic properties have been investigated, such as the additive graphite, doped amount and calcination temperature. After being calcined at appropriate temperature, the graphite was totally decomposed and catalysts of irregular bulk-type structure were converted to uniform nanoplate materials. The catalytic activity of as-prepared catalysts was evaluated by the benzyl alcohol selective oxidation and the simulation gasoline desulfurization. It is proved that transition metal Cu/Fe-codoped tungstosilicates are more active than the corresponding undoped compounds under mild conditions and Cu/Fe-doped amount greatly impacted the catalytic activity, and Cu1.00Fe1.00SiW11 sample exhibited the best catalytic activity with 98.0% conversion and 98.3% selectivity in benzyl alcohol selective oxidation into benzaldehyde at 80°C only for 60min, and above 98% of the desulfurization rate at 65°C just for 80min.