In this study, the Mn2O3@In2O3 core-shell structures were prepared by a two-step hydrothermal method for TEA detection. Characterization of the morphological composition reveals that Mn2O3@In2O3 is a microsphere structure with Mn2O3 as the core and In2O3 as the shell. The results of the gas-sensitive performance tests showed that the response of Mn2O3@In2O3 to 100 ppm TEA was 47 at 180 °C, which was a significant improvement over the original In2O3, and it had excellent long-term stability and reproducibility. The improved gas-sensitive properties are due to the special structure of the core-shell material and the successful construction of p-n heterojunctions between the interfaces.