Molybdenum disulfide (MoS2) has been intensively investigated for its high theoretical capacity as an advanced anode material for lithium storage. However, the low electronic conductivity and frail layered structure give rise to its poor cycling stability and low rate performance. Herein, by taking advantages of the porous structure and the high N content of metal-organic frameworks (MOFs) derivatives, a facile and scalable method combining electrospinning and following a hydrothermal process was developed to fabricate MoS2-based composite fibers, in which ultrathin MoS2 nanoplates were vertically assembled on the polyacrylonitrile-MOF-derived N-doped porous carbon nanofibers (PCNF). As expected, benefiting from the hierarchical structure of PCNF and the synergies between MoS2 and PCNF, the obtained PCNF@MoS2 exhibited high capacity and cycling performance in a lithium battery.