The improvement of catalytic efficiency is of great significance to the removal of volatile organic compounds (VOCs), a class of key air pollutants leading to ground-level ozone pollution. Herein, a series of micro-spherical Ca-Mn mixed oxides (CaxMnyOz), namely CaMn3O6, Ca2Mn3O8 and CaMnO3, were prepared by a two-step precipitation method, and defects were constructed on which by selective dissolution to enhance the low-temperature catalytic performance in the oxidation of propane (C3H8) as a representative short-chain alkane VOCs. The synthesized CaxMnyOz oxides demonstrated drastically different response to the dissolution modification initiated by acid treatment. Specifically, after acid dissolution, while CaMn3O6 and Ca2Mn3O8 maintained largely their original structures, the perovskite-type CaMnO3 underwent lattice rearrangement and was transformed into γ-MnO2-like product with only a tiny amount of Ca. In C3H8 oxidation, the catalytic performance of CaMnO3 was significantly improved after selective dissolution, as indicated by a significant decrease of T90, i.e. the temperature to achieve 90% C3H8 conversion, from 455 °C to 240 °C. Mechanistic investigation by in-depth X-ray photoelectron spectroscopy studies revealed that selective dissolution led to higher Mn4+ concentrations and more oxygen vacancies on the oxide surfaces, thus facilitated electron transfer and O2 activation in C3H8 oxidation reactions. This study paves a new path for the design of cost-effective oxide catalysts toward the abatement of short-chain alkane VOCs.