A nanowire-directed templating synthesis of metalorganic framework (MOF) nanofibers has been demonstrated, where ultrathin tellurium nanowires (TeNWs) with excellent dispersivity can act as templates for directed growth and assembly of ZIF-8 nanocrystals (one typical MOF), resulting in the formation of uniform ZIF-8 nanofibers. The as-obtained ZIF-8 nanofibers can be conveniently converted into highly porous doped carbon nanofibers by calcination. Compared with bulk porous carbon by direct carbonization of MOF crystals, these doped carbon nanofibers exhibit complex network structure, hierarchical pores, and high surface area. Further doped by phosphorus species, the co-doped carbon nanofibers exhibit excellent electrocatalytic performance for oxygen reduction reaction, even better than the benchmark Pt/C catalyst.