Metallic Sn has high conductivity and high theoretical capacity for lithium storage but it suffers from severe volume change in lithiation/delithiation leading to capacity fade. Yolk-shell and core-shell Sn@C spheres interconnected by carbon nanofibers were synthesized by thermal vapor and thermal melting of electrospun nanofibers to improve the cycling stability. Sn particles in yolk-shell spheres undergo dynamic structure evolution during thermal melting to form core-shell spheres. The core-shell spheres linked along the carbon nanofibers show outstanding performance and are better than the yolk-shell system for lithium storage, with a high capacity retention of 91.8% after 1000 cycles at 1 A g-1. The superior structure of core-shell spheres interconnected by carbon nanofibers has facile electron conductivity and short lithium ion diffusion pathways through the carbon nanofibers and shells, and re-develops Sn@C structures with Sn clusters embedded into carbon matrix during electrochemical cycling, enabling the high performance.