Exceptional capacities and excellent rate performance have been achieved by anodes made from electrospun carbon nanofibers (CNFs) that possess synergies of (i) functionalization with carbonyl and carboxyl groups, (ii) presence of nanopores and (iii) embedded graphene layers. The Fe precursor incorporated into the polyacrylonitrile melt functions as both catalyst for graphitization and sacrificial phase. CNFs are functionalized and nanopores surrounded by graphene layers are simultaneously created during the chemical etching of Fe3C particles from the CNFs. The pore size and volume could be tuned by controlling the Fe precursor content. Both the functional groups and nanopores are accessible to Li ions, and the satisfactory electrical conductivity arising from graphitization allows fast transfer of electrons. Remarkable capacities of 983 and 318 mAh g−1 are obtained when discharged at 100 and 3000 mA g−1, respectively, along with excellent capacity retention after 100 cycles.