Efficient and non-Pt catalysts are highly desirable for many kinds of electrochemical applications. Herein, we have investigated the free-standing nitrogen-doped carbon nanotubes/carbon nanofibers composite (NCNT/CNFs) as an efficient cathode catalyst for the oxygen reduction reaction (ORR). The composite with a hierarchical structure is prepared by the pyrolysis of pyridine over flexible electrospun carbon nanofibers film (CNFs) supported with the nano-Fe catalyst. Scanning electron microscopy and transmission electron microscopy characterizations indicated that the curved NCNTs are sparsely, but tightly distributed on CNF surface. The as-prepared composite displayed good catalytic activity for ORR in an alkaline medium, with a favorable four-electron pathway, better long-term stability (94.6% retention after 10000 s), selectivity and resistance to the methanol crossover compared to the powder-form NCNTs and commercial Pt/C catalyst. The improved electrochemical performance of the NCNT/CNFs can be mainly attributed to the pyridinic-N doping and unique three-dimensional network structure. The results indicate that this novel composite can be used as a promising Pt-free ORR electrocatalyst.