Three-dimensional (3D) MnO2/Carbon Sphere (MnO2/CS) composite was synthesized from zero dimensional carbon spheres and one-dimensional alpha-MnO2 using hydrothermal method. The hierarchical MnO2/CS composite was applied for the catalytic oxidation and adsorption of elemental mercury (Hg-0) from coal-fired flue gas. The characterization results indicated that this composite exhibits a 3D urchin morphology. Carbon spheres act as the core and alpha-MnO2 nano-rods grew on the surface of carbon spheres. This 3D hierarchical structure benefits the enlargement of surface areas and pore volumes. Hg-0 removal experimental results indicated that the MnO2/CS composite has an outstanding Hg-0 removal performance due to the higher catalytic oxidation and adsorption performance. MnO2/CS composite had higher than 99% Hg-0 removal efficiency even after 600 min reaction. In addition, the nano-sized MnO2/CS composite exhibited better SO2 resistance than pure alpha-MnO2. Moreover, the Hg-TPD results indicated that the adsorbed mercury can release from the surface of MnO2/CS using a thermal decomposition method. (C) 2017 Elsevier B.V. All rights reserved.