Ordered mesoporous In2O3 gas-sensing materials with controlled mesostructured morphology and high thermal stability have been successfully synthesized via a nanocasting method in conjunction with the container effect. The mesostructured ordering, as well as the particle size, crystallinity and pore size distribution have been proved to vary in a large range by using the XRD, SAXRD, SEM, TEM, and nitrogen physisorption techniques. The control of the mesostructured morphology was carried out by tuning the transportation rate of indium precursor in template channel resulting from the different escape rate of the decomposed byproducts via the varied container opening and shapes. The particular relation between the mesostructured ordering and gas sensing property of mesoporous In2O3 was examined in detail. It was found that the ordered mesoporous In2O3 with appropriate mesostructured morphology exhibited significantly improved ethanol sensitivity, response and selectivity performances in comparison with the other ordered mesoporous In2O3, which benefits from the large surface area with enough sensing active sites, proper pore distribution for sufficient gas diffusion, and appropriate particle size for effective electron depletion. The resulting sensing behaviors lead to a better understanding of designing and using such mesoporous metal oxides for a number of gas-sensing applications.