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A novel and facile approach was developed for the fabrication of amorphous double-shelled zinc–cobalt citrate hollow microspheres and crystalline double-shelled ZnCo₂O₄ hollow microspheres. In this approach, amorphous double-shelled zinc–cobalt citrate hollow microspheres were prepared through a simple route and with an aging process at 70 °C. The combining inward and outward Ostwald ripening processes are adopted to account for the formation of these double-shelled architectures. The double-shelled ZnCo₂O₄ hollow microspheres can be prepared via the perfect morphology inheritance of the double-shelled zinc–cobalt citrate hollow microspheres, by calcination at 500 °C for 2 h. The resultant double-shelled ZnCo₂O₄ hollow microspheres manifest a large reversible capacity, superior cycling stability, and good rate capability.