In this paper, pure-phase ZnMnO3 porous spherulites are uniquely synthesized through the thermal decomposition of Zn-Mn binary carbonate precursors facilely co-precipitated at room temperature, possessing an average diameter of 1.2±0.3μm and acquiring porosity with a specific surface area of 24.3m2 g−1. When tentatively applied as lithium-ion battery anodes for the first time, these porous spherulites deliver an initial discharge capacity of 1294mAhg−1 at 500mAg−1 and retain an reversible value of 879mAhg−1 over 150 cycles. By comparison, the equimolar powder mixture of nano-sized ZnO and MnO2 synergistically shows a higher lithium storage capability than the two unary transition metal oxides, but lower than anode material ZnMnO3. Aside from its nanostructured characteristics, an inner atomic synergistic effect within the cubic lattices may account for the superior electrochemical performance of well-crystallized ZnMnO3.