N-doped amorphous carbon coated Fe3O4/SnO2 coaxial nanofibers were prepared via a facile approach. The core composite nanofibers were first made by electrospinning technology, then the shells were conformally coated using the chemical bath deposition and subsequent carbonization with polydopamine as a carbon source. When applied as a binder-free self-supported anode for lithium ion batteries, the coaxial nanofibers displayed an enhanced electrochemical storage capacity and excellent rate performance. The morphology of the interwoven nanofibers was maintained even after the rate cycle test. The superior electrochemical performance originates in the structural stability of the N-doped amorphous carbon shells formed by carbonizing polydopamine.