This paper presents the catalytic decomposition of CS2 using dielectric barrier discharge plasma coupled with novel limonite or siderite supported BiVO4 composite material (limonite/BiVO4 or siderite/BiVO4) prepared via a hydrothermal method. The crystalline structure, surface morphology, gas adsorption properties, and surface chemistry of the catalysts are characterized. The results show that BiVO4 supported on the limonite or siderite is highly dispersible, which increases its active site. In addition, CS2 decomposition efficiencies obtained using catalysts fabricated with various Fe/Bi ratios and calcination temperatures are experimentally evaluated. The result show that the maximum CS2 decomposition efficiencies are obtained using catalysts calcined at 350°C with limonite/BiVO4 and siderite/BiVO4 mass ratios of 3:7, which respectively yield CS2 decomposition efficiencies are 11.9% and 13.2% greater than that obtained with dielectric barrier discharge treatment alone. The differences in the CS2 decomposition efficiencies of the two types of supported catalysts may be due to the chemical and physical differences between limonite and siderite, including the oxidation states of iron and the surface morphology of the iron ores.