In this study, the synthesis of a novel catalyst WO3/MoCl5 was carried out by the thermal method. The method gave an entirely different product compared to previous studies that doped Mo on the surface of semiconductor metal oxides. The degradation reaction of crystal violet (CV) and rhodamine B (RB) dye were done without any energy source. The results showed an incomparably superior result for degradation, with a reaction rate constant of 1.74 s−1 for 30 ppm CV, 1.08 s−1 for 30 ppm RB, and a higher value than 1 s−1 for both cases of 50 ppm dye solution. To the author’s knowledge, this catalyst has the highest reaction rate compared to other studies that targeted CV and RB, with an immense reaction rate increase of more than 100 times. Reusability of the three trials was verified, and the only process required was washing the catalyst after the reaction. One of the drawbacks of the advanced oxidation process (AOP), which has a degradation percent limit, has been solved, since 100% mineralization of the dye was available using this catalyst. FT-IR spectroscopy revealed that W-O-Mo linkage was successfully processed while Mo-Cl linkage has retained. 1H-NMR spectroscopy results confirmed that the degradation product of the dye treated by simple MoCl5 and WO3/MoCl5 was different. Deep inspection of specific regions of NMR fields gave necessary information about the degradation product using WO3/MoCl5.