A three-dimensional porous core-shell Sn@carbon anode on nickel foam substrate was fabricated by electrostatic spray deposition (ESD) technique followed by high temperature treatment. The carbon shell with a thickness of about 3.2 nm was formed on porous Sn structure at high temperature. 3D porous structure and carbon shell were designed to buffer volume expansion/shrinkage of Sn lattice upon cycling and increase the electrical conductivity. After 315 charge/discharge cycles Sn@carbon anode exhibited high specific capacity of 638 mAh g−1 with the low capacity fade of average 0.11 mAh g−1 per cycle. Sn@carbon based anodes was demonstrated to have promising potential for high performance lithium ion batteries application.