Uniform Mn(2)O(3) octahedral nanoparticles were synthesized by a mediated N, N-dimethylformamide (DMF) solvothermal route. On the basis of a time-dependent experiment, we propose that the Mn(2)O(3) octahedra were formed through oriented aggregation of primary nanocrystals. Meanwhile, poly(vinyl-pyrrolidone) (PVP) was applied as a surfactant to facilitate the oriented aggregation of small Mn(2)O(3) nanoparticles into octahedral crystallites. By tuning the amount of Mn(NO(3))(2), particles with average sizes 1 µm to 300 nm, with a narrow size distribution, could be fabricated. The catalytic test results show that the as-obtained Mn(2)O(3) octahedra exhibited desirable CO catalytic oxidation properties and the surface texture and particle size significantly affected the catalytic activity. By contrast, the larger Mn(2)O(3) octahedral nanoparticles prepared at a lower concentration of Mn(NO(3))(2) exhibited relatively high activities.