Herein, we report a simplistic method to fabricate the surface-oxidized cobalt phosphide (CoP) nano crystals (NCs), which is used as electrocatalyst for oxygen reduction reaction (ORR) in microbial fuel cell (MFC) for the first time. The corallite-like CoP NCs are successfully prepared by a hydrothermal reaction following a phosphating treatment in N-2 atmosphere. When used as an ORR catalyst, cobalt phosphide shows comparable onset potential, inferior resistance, as well as a small Tafel slope with long-term stability in neutral media. The maximum power density of MFC embellished with 10% CoP reached 1914.4 +/- 59.7 mW m(-2), which is 108.5% higher than the control. The four-electron pathway, observed by the RDE, plays a crucial role in electrochemical catalytic activity. In addition, material characterizations indicate that the surface oxide layer (CoOx) around the metallic CoP core is important and beneficial for ORR. Accordingly, it can be expected that the as-synthesized CoP will be a promising candidate of the non-precious metal ORR electrocatalysts for electrochemical energy applications. (C) 2017 Published by Elsevier B.V.