Designing transition metal composite oxide catalysts with high catalytic performance and stability in the catalytic oxidation of CVOCs is still a big challenge, especially by economic and convenient methods. To realize this, highly dispersed MnCoOx nanoparticles were prepared on the HZSM-5 to synthesize MnyCozOx/H5-50 catalyst and applied in the catalytic oxidation of 1,2-dichloroethane (1,2-DCE). The T90 of Mn1Co1Ox/H5-50 (215 °C) decreased by 53 and 45 °C compared with Mn2O3/H5-50 and Co3O4/H5-50, respectively. The outstanding catalytic activity and thermal stability of Mn1Co1Ox/H5-50 are attributed to the abundance of Mn4+, Co2+, and adsorbed oxygen, prominent redox ability, and suitable acidity. All of these features originated from the strong interaction in the highly dispersed MnCoOx solid solution. The DFT confirmed that the MnCoOx activated the C-Cl bond to accelerate the occurrence of dechlorination reactions and reduce the formation of intermediate products. In-situ DRIFTS proved that the elimination rate of vinyl alcohol or vinyl chloride intermediate was the key rate-determining step in the reaction process. The prepared Mn1Co1Ox/H5-50 catalyst could precisely achieve this objective at high temperature region and subsequently reduce the production of toxic by-products. This work provides valuable insights into the design of efficient and economical catalysts for the degradation of CVOCs.