Herein, cesium was introduced into two kinds of rod-shaped α-MnO2 with different crystal facets by ion exchange technique, and the as-prepared four catalysts were used to evaluate their performance in the total combustion of ethanol with low concentration. When compared to undoped α-MnO2(211) and α-MnO2(310) catalysts, the Cs-doped α-MnO2(211)-Cs and α-MnO2(310)-Cs catalysts showed significantly improved catalytic performance at a high space velocity (SV) (132,000 mL/(g·h)). Kinetic results demonstrate that in catalysts the activation energy (Ea) with Cs dopant is lower than without. The characterization results by various techniques such as XRD, ICP-OES, BET, FE-SEM, HR-TEM, H2-TPR, NH3-TPD, XPS, and ethanol-TPD reveal that the introduction of Cs into α-MnO2 samples not only improves the low temperature reducibility but also contributes to the generation of more surface Mn4+ and oxygen vacancies, which are efficient in forming more reactive oxygen species, therefore, boosting ethanol oxidation activity. The incorporation of the alkali cation Cs+ into the α-MnO2 is an effective strategy in designing low-cost, high-performance, and environmentally friendly metal oxide combustion catalysts.