W@WO3 Nanostructured films on carbon cloth was grown by the method of high temperature reactive thermal evaporation without catalyst and magnetron sputtering. The results of XRD, SEM and XPS show that the structure of the sample with good crystallinity, and the W particles adsorbed on WO3 nano film to form the structure W@WO3 Ohmic junction can be used to improve the charge separation efficiency of semiconductor materials. When the sample was exposed to Rhodamine B (RB) solution for 5 hours, 76% of Rb could be degraded. Compared with WO3 nanostructure with 26% degradation efficiency, the photocatalytic performance of the sample film modified by W could be greatly improved. In this experiment, carbon cloth was used as substrate to grow nano films with large specific surface area, which can provide more active sites for photocatalytic reaction. The experiment does not need expensive noble metal modification and catalyst. It can provide an effective preparation method for the preparation of high-quality photocatalytic materials with low cost, and has a broad application prospect in the field of wastewater treatment and degradation.