Nitrogen doped carbon nanomaterials are excellent electrode materials and catalysts due to their extraordinary conductivity, prolific structures, and abundant active sites. Herein, two kinds of waste biomass, catkins and Okara were used as precursors for the preparation of novel nitrogen doped carbon fibers via hydrothermal and pyrolysis process. The blend of nitrogen-rich Okara with catkins effectively enhanced the content of doped nitrogen in the product. The as-prepared sample (denoted as NCF900) exhibited a hollow fiber like structure with a diameter of 2 to 5 mu m and had abundant highly active sites of pyridinic N and graphitic N, thereby improving its electrocatalytic activity in oxygen reduction reaction (ORR). The typical rotating disk electrode test proved that the NCF900 exhibited a high onset potential (0.82 V vs RHE) and a nearly four-electron pathway for ORR in alkaline solution as well as stronger methanol tolerance and better long-term durability than commercial Pt/C. The green, low cost synthetic method and the excellent ORR catalytic efficiency of NCF900 made it a promising electrocatalytic material for the ORR in fuel cells.