A 3D hierarchical porous ceramic electrode is fabricated directly from a carbon-oxides precursor by a general, cost-effective, and facile method. The oxygen reduction reaction activity of the electrode is significantly enhanced due to enlarged active areas and optimized gas transport channels. For the first time, this study demonstrates that a cobalt-free cathode is able to reach the target area specific resistance value of 0.15 Ω cm2 at 600 °C. The new material has been successfully used as the cathode for a SOFC and shows high power generation ability below 600 °C.