Multifunctional Au(core)Co(3)O(4shell) nanocubes were synthesized through the introduction of chloroauric acid (HAuCl(4)) into a typical hydrothermal system after a solvothermal process was completed to form metastable Co(3)O(4) hollow nanospheres in the presence of sodium dodecyl benzenesulfonate (SDBS), which served as the surfactant. The strategy suggested that HAuCl(4) played a vital role in the shape transformation and core/shell structure formation, and the sizes of the nanocubes can be tunable through control of the acid concentration. The core/shell structure of the nanocubes was demonstrated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and element analysis (EA) measurements. Moreover, Li ion battery measurement indicated that trace Au intercalation altered not only the size and shape of the Co(3)O(4) nanoparticles but also greatly increased their electrochemical properties. These multifunctional nanocubes will be not only helpful to study physical chemistry properties of magnetic nanocrystals but also are expected to find use in many fields such as biomolecular detection and analysis, sensor, electrochemistry, and Li ion batteries.