Carbon spheres (CSs) with an average diameter of around 500∼700nm are prepared by a extended Stöber method. Urchin-like MnO2 nanorods were deposited on the carbon spheres by hydrothermal method and the thickness of α-MnO2 shell is about 700∼800nm. Pd particles with a diameter of around 8∼15nm are dispersed on the surface of vertically aligned α-MnO2 rods which have a diameter of 40∼50nm. Three-dimensional (3D) Pd-MnO2/CS shows better activity and stability than Pd/CS and MnO2/CS for anodic oxygen evolution reaction (OER) in water electrolysis, which shows that Pd-doped urchin-like CS-MnO2 core-shell structure material would be a superiority catalyst for the OER. The onset potential shifts negatively and current density improves on the Pd-MnO2/CS for the OER, showing a synergistic effect between Pd and MnO2.