This study examined the combination of activated carbon and magnetite with calcium peroxide in enhancing the anaerobic digestion (AD) performance of food waste (FW). The individual mechanisms of these two approaches were also clarified. The results indicated that AC/CaO2 achieved the highest specific methane yield of 434.4 mL/g VS, followed by Fe3O4/CaO2 (416.9 mL/g VS). Both were significantly higher than other groups (control, AC, Fe3O4, and CaO2 were 330.1, 341.4, 342.8, and 373.2 mL/g VS, respectively). Additionally, compared to Fe3O4/CaO2, AC/CaO2 further increased reactive oxygen species (ROS), thereby enhancing the hydrolytic acidification process. Simultaneously, the higher ROS levels of Fe3O4/CaO2 and AC/CaO2 promoted the formation of microbial aggregates and established a more robust enzymatic defense system and unique damage repair strategy. The research comparatively analyzed the synergistic mechanism of iron-based and carbon-based conductive materials with CaO2, providing new perspectives for optimizing the AD of FW.