Mixed/composite oxides of transition metals with hollow structures, especially multishelled hollow architecture, have promising potential for different applications, but their syntheses still remain a big challenge. Herein, a facile coordination polymer precursor method was developed to construct various multishelled Zn-Mn-O hollow micro-spheres, including Zn-Mn-O-3, ZnMn2O4, and ZnMn2O4/Mn2O3. The composition of the hollow structures can be adjusted by controlling the composition of the coordination polymer precursors, which are easily obtained with Zn2+, Mn2+, and salicylic acid under solvothermal conditions. With a simple programmable heating process, the shell of the hollow structures can be adjusted and double-/triple-shelled ZnMnO3, ZnMn2O4, and ZnMn2O4/Mn2O3 hollow microspheres have been controllably obtained. When the triple-shelled ZnMn2O4 hollow microspheres are used as anode materials for lithium-ion batteries, excellent activity and enhanced stability can be achieved. The triple-shelled hollow ZnMn2O4 exhibits a reversible capacity of 537 mA.h.g(-1) at 400 mA.g(-1) and a nearly 100% capacity retention after 150 cycles. This strategy is facile and scalable for the production of high-quality complex hollow nanostructures, with the possibility of extension to the preparation of other mixed metal oxides with complex structures.