Microwave-assisted processing has shown tremendous promise in accelerating chemical reactions and reducing energy consumption through targeted dielectric heating. This study develops MOF-derived Mn-Co and Ce-Co oxide catalysts for energy-efficient benzene oxidation via microwave catalysis. The MnCo spinel oxides (particularly MnCo11-400) exhibit superior microwave absorption and catalytic activity due to enhanced oxygen mobility and tailored dielectric properties. Microwave irradiation enables rapid benzene mineralization over the MnCo11-400 catalyst, achieving 78% conversion at 30 W and complete conversion at 50 W, demonstrating exceptional energy efficiency at low power inputs. Microwaves significantly lower the reaction temperature compared to conventional thermal catalysis (ΔT = 100–250 °C). Stability tests confirm robustness over repeated power cycling (80% conversion retained after 3 × 1 h on/off cycles). Furthermore, an adsorption–microwave oxidation synergistic strategy is demonstrated: pre-adsorbed low-concentration benzene (1.15 mmol) at ambient temperature undergoes complete mineralization within 20 min under 30 W microwave irradiation. The intermittent microwave operation achieves equivalent benzene removal to continuous thermal processing while significantly reducing energy demand. This work establishes MOF-derived spinel oxides as high-performance microwave catalysts for low-temperature VOC abatement.