One of the major problems in the development of lithium-ion batteries is the relatively low capacity of cathode materials compared to anode materials. Owing to its high theoretical capacity, vanadium oxide is widely considered as an attractive cathode candidate. However, the main hindrances for its application in batteries are its poor capacity retention and low rate capability. Here, we report the development of multi-shelled vanadium oxide hollow microspheres and their related electrochemical properties. In contrast to the conventional cation-adsorption process, in which the metal cations adsorb on negatively charged carbonaceous templates, our approach enables the adsorption of metal anions. We demonstrate controlled syntheses of several multi-shelled metal oxide hollow microspheres. In particular, the multi-shelled vanadium oxide hollow microspheres deliver a specific capacity of 447.9 and 402.4 mAh g−1 for the first and 100th cycle at 1,000 mA g−1, respectively. The significant performance improvement offers the potential to reduce the wide capacity gap often seen between the cathode and anode materials.