Nitric oxide (NO) can pose a severe threat to human health and the environment. Many catalytic materials that contain noble metals can oxidize NO into NO2. Therefore, the development of a low-cost, earth-abundant, and high-performance catalytic material is essential for NO removal. In this study, mullite whiskers on a micro-scale spherical aggregate support were obtained from high-alumina coal fly ash using an acid–alkali combined extraction method. Microspherical aggregates and Mn(NO3)2were used as the catalyst support and the precursor, respectively. A mullite-supported amorphous manganese oxide (MSAMO) catalyst was prepared by impregnation and calcination at low temperatures, in which amorphous MnOxis evenly dispersed on the surface and inside of aggregated microsphere support. The MSAMO catalyst, with a hierarchical porous structure, exhibits high catalytic performance for the oxidation of NO. The MSAMO catalyst, with a 5 wt% MnOxloading, presented satisfactory NO catalytic oxidation activity at 250 °C, with an NO conversion rate as high as 88%. Manganese exists in a mixed-valence state in amorphous MnOx, and Mn4+provides the main active sites. The lattice oxygen and chemisorbed oxygen in amorphous MnOxparticipate in the catalytic oxidation of NO into NO2. This study provides insights into the effectiveness of catalytic NO removal in practical industrial coal-fired boiler flue gas. The development of high-performance MSAMO catalysts represents an important step towards the production of low-cost, earth-abundant, and easily synthesized catalytic oxidation materials.