It was found that a series of spinel CoCr2O4 oxides were very active and selective for dichloromethane combustion, and the best performance was obtained on a catalyst calcined at 600°C (with a areal specific reaction rate of 3.41×10−8molCH2Cl2s−1m−2 at 220°C). Quantitative analyses revealed that Cr3+/Cr6+ cations could partially substitute Co3+ cations in the octahedral sites of the spinel oxide at high-temperature calcination and thus to enhanced reducibility and surface acidity of the oxide, which synergistically governed the observed catalytic behaviors. Moreover, it was found that high valent Cr species (Cr6+) played very important role in the reaction, with a much higher turnover frequency (2.2×10−3s−1) than that of the Cr3+ (0.56×10−3s−1).