ZnO–ZnCo2O4 hybrid hollow microspheres are successfully produced via an annealing process of the pre-fabricated zinc–cobalt citrate hollow microspheres in air. ZnO and ZnCo2O4 have homogeneous distribution within the whole hollow microspheres. The gained hybrid hollow microspheres deliver outstanding lithium storage properties when utilized as the anode material in lithium ion batteries. A high reversible capacity of 1199mAhg−1 can be retained after 200 cycles. The exceptional electrochemical properties of the hybrid hollow microspheres are ascribed to the synergetic effect between ZnO and ZnCo2O4 nanoparticles, the catalytic effect of Co nanocrystals, the favorable hollow structures together with the nanometer-sized building blocks of hybrid microspheres.