To efficiently improve the attractive properties of electrode material for lithium ion batteries (LIBs), the uniform hybridization of 2 Dimensional WS2 nanosheets of nitrogen doped carbon nanofiber (WN-CNF) as a novel anode electrode is synthesized via a facile electrospinning strategy. The well-aligned structure, roughness of surface morphology and chemical composition are characterized by microscopic and spectroscopic analysis. Nitrogen-containing groups and 1 T phase of WS2 in WN-CNF are demonstrated as the electro-active sites to enhance the capacitive performance. Meanwhile, WN-CNF exhibits a highly reversible specific capacity of 814 mAh g−1 at the current density of 100 mA g−1, excellent rate capability of 52% from 100 to 1000 mA g−1 and cyclic stability of 87% after 120 charge/discharge cycles. The high performance can be attributed to the synergistic effects of rough surface, heteroatom N incorporation and hybridization with pseudocapacitive 2D WS2.