Mesocrystals are of great importance owing to their novel hierarchical microstructures and potential applications. In the present work, a simple additive-free method has been developed for the controllable synthesis of manganese monoxide (MnO) mesocrystals, in which cheap manganese acetate (Mn(Ac)2) and ethanol were used as raw materials without involving any other expensive additives such as surfactants, polyelectrolyte, or polymers. The particle size of the resulting MnO mesocrystals is tunable in the range 400-1500 nm by simply altering the concentration of Mn(Ac)2 in ethanol. The percentage yield of the octahedral MnO mesocrystals is about 38 wt % with respect to the starting Mn(Ac)2. The selective adsorption of oligomers, which was resulted from the polymerization of ethanol, acted as an important role for the mesocrystal formation. A mechanism involving the oriented aggregation of MnO nanoparticle subunits and the subsequent ripening process was proposed. Moreover, for the first time, the as-synthesized MnO mesocrystals were employed as a novel template to fabricate functional materials with an octahedral morphology including MnO@C core/shells, carbon, and graphitic hollow octahedrons. This method shows the importance of mesocrystals not only for the field of material research but also for the application in functional materials synthesis.