Novel ZnMn2O4 ball-in-ball hollow microspheres are fabricated by a facile two-step method involving the solution synthesis of ZnMn-glycolate hollow microspheres and subsequent thermal annealing in air. When evaluated as an anode material for lithium-ion batteries, these ZnMn2O4 ball-in-ball hollow microspheres show significantly enhanced electrochemical performance with high capacity, excellent cycling stability and good rate capability.