A nitrogen-riched monomer (10,12-bis(4-hexylthiophen-2-yl)thieno[3',4':5,6]pyrazino[2,3-f][1,10] phenanthroline) (HTPP) was synthesized and polymerized to give a polymer (PHTPP) on the electrode directly by the electrodeposition method. The polymer-Cu complex (PHTPP-Cu) was obtained by immersing the polymer modified electrode in copper sulfate solution. The PHTPP-Cu catalyst provides two types of active sites including pyridinic-N atoms and Cu-N-x-C units, and also has a high specific surface area and better conductive property. These excellent features facilitate the reduction of oxygen to water by the catalyst through a four-electron mechanism in the phosphate buffer solution (PBS). Be employed as the cathodic catalyst, PHTPP-Cu also exhibits excellent performance in microbial fuel cell (MFC), which was comparable to the commercial Pt/C catalyst. Such a polymer based catalyst providing a good opportunity for the preparation of low-cost non-noble metal ORR catalyst for fuel cell utilization. (C) 2017 Elsevier B.V. All rights reserved.