Development of cheap, abundant and noblemetal-free materials as high efficient oxygen reduction electrocatalysts is crucial for future energy storage system. Here, one-dimensional (1D) MnO N-doped carbon nanofibers (MnO-NCNFs) were successfully developed by electrospinning combined with high temperature pyrolysis. The MnO-NCNFs exhibit promising electrochemical performance, methanol tolerance, and durability in alkaline medium. The outstanding electrocatalytic activity is mainly attributed to several issues. First of all, the uniform 1D fiber structure and the conductive network could facilitate the electron transport. Besides, the introduction of Mn into the precursor can catalyze the transformation of amorphous carbon to graphite carbon, while the improved graphitization means better conductivity, beneficial for the enhancement of catalytic activity for oxygen reduction reaction (ORR). Furthermore, the porous structure and high surface area can effectively decrease the mass transport resistance and increase the exposed ORR active sites, thus improve utilization efficiency and raise the quantity of exposed ORR active sites. The synergistic effect of MnO and NCNFs matrix, which enhances charge transfer, adsorbent transport, and delivers efficiency in the electrolyte solution, ensures the high ORR performance of MnO-NCNFs.