The objective of this study was to compare the transformation of by-products between single dielectric barrier discharge (SDBD) and double dielectric barrier discharge (DDBD), to optimize the preparation of graphene-based catalysts and apply them in combination with DBD for volatile organic compound degradation. We compared the degradation performance of SDBD and DDBD, prepared, and characterized graphene-based catalysts. SEM, BET, XRD, and FTIR analyses showed that the morphologies and internal structures of the three catalysts were the best when 0.25mL of [BMIM]PF6 was added. When MnOx/rGO, FeOx/rGO, and TiOx/rGO were used in combination with DDBD, the degradation rates of benzene were found to be 83.5%, 77.2%, and 63.8%, respectively, whereas the O3 transformation rates were 60%, 79%, and 40%, respectively. Moreover, the NO2 transformation rates were 70%, 55%, and 42.5%, respectively, whereas the NO transformation rates were 69%, 39%, and 33.5%, respectively. The CO2 selectivity was 62%, 51%, and 49%, respectively. MnOx/rGO exhibited superior performance in the degradation of benzene series, NO transformation, NO2 transformation, CO2 selectivity, and energy efficiency. On the other hand, FeOx/rGO exhibited superior performance for O3 transformation. Based upon the XPS analysis, it was found that Mn3O4 and Fe3O4 played a leading role in promoting the degradation of benzene series and the transformation of by-products.