Self-supported 3-demensional (3D) nitrogen-doped bimodal-pore structured carbon fiber aerogel is synthesized via a facile carbonization process using prawn shell as the raw material. The fabricated N-doped carbon fiber aerogel possesses micro- and meso-porous pores with an N doping level of 5.9% and a high surface area of 526 m2 g- 1. As an electrocatalyst, the resultant N-doped carbon fiber aerogels exhibits superior electrocatalytic activity towards oxygen reduction reaction (ORR) with a more positive ORR onset-potential, better stability and high resistance to crossover effect compared to the commercial Pt/C electrocatalyst.