Hierarchical manganese oxides with enhanced catalytic performance have been successfully synthesized via simple thermal annealing of manganese coordination polymer precursors, which is a facile, cost-effective, and environmentally benign preparation method. The resultant manganese oxide particles formed hierarchical structures with a starfish-like morphology and exhibited enhanced low-temperature SCR performance below 200 °C without dopants or supporting materials. In addition, the morphology, chemical states, crystal structure and acidity of manganese oxide catalysts prepared at different calcination temperatures were investigated. It is elucidated that enhanced SCR catalytic performance was strongly dependent on the hierarchical morphology of the catalysts.