Three ZnO-C samples with distinct structures including yolk-shell microspheres, hollow microspheres and solid microspheres are fabricated through a facile chemical solution reaction followed by calcination in argon. When employed as the anode materials for lithium ion batteries, yolk-shell ZnO-C microspheres exhibit the best electrochemical properties than the hollow and solid microspheres. After 150 cycles, yolk-shell ZnO-C microspheres demonstrate a relative high capacity of 520mA h g−1 at a current density of 100mAg−1 with a Coulombic efficiency of about 99.3%. The excellent cycling stability and good rate capability of yolk-shell ZnO-C microspheres stem from the synergistic effect of the unique yolk-shell structures and extra carbon support.