High-quality porous ZnMn2O4 microspheres composed of interconnected nanoparticles have been achieved by calcination of metal carbonates synthesized by a solvothermal reaction. The porous microspheres are characterized by XRD patterns, SEM, TEM, and HRTEM images to reveal the crystal phase and particle morphology. The porous structure and nanoscale building blocks of ZnMn2O4 microspheres make them a promising anode material for lithium ion batteries. After 300 cycles at a current density of 500mAg−1, they still preserve a reversible capacity of 800mAhg−1. Even at 2Ag−1, the reversible capacity could be 395mAhg−1, higher than the theoretical capacity of graphite. The superior electrochemical performances can be associated with the porous structure and nanoscale building blocks, which promote the contacting between electrolyte and electrode, accommodate volume change during discharge/charge processes, and provide a large number of active surface sites for lithium storage.