Due to its distinctive structure and properties, MFe2O4 has been extensively investigated in catalytic oxidation. In this study, we synthesized a ternary metal composite Fe-based spinel catalyst using the sol-gel method for toluene oxidation. The catalytic performance assessments showed that the catalytic performance of Cu0.7Co0.3Fe2O4 (T90 = 262 °C, 100,000mL·g-1·h-1) was superior to that of CuFe2O4 (T90 = 270 °C) and CoFe2O4 (T90 = 310 °C), compared to binary metal spinel catalysts. The characterization results indicate that the strong interactions among Cu, Co, and Fe in the ternary metal composite structure increased the content of oxygen vacancy at lower temperatures, thereby increasing the content of surface reactive oxygen species and improving catalytic performance. This study highlights the potential application of Fe-based spinel structures to develop more efficient spinel catalysts.