Nanocrystalline Co3O4 thin-film anodes were deposited on Pt-coated silicon and 304 stainless steel by radio frequency (RF) magnetron sputtering. The as-deposited and annealed cobalt oxide thin films showed smooth and crack-free morphologies. Both the as-deposited and annealed films exhibited spinel Co3O4 phase with nanocrystalline structure. High-temperature annealing enhanced the crystallinity of RF-sputtered cobalt oxide films due to rearrangement of cobalt and oxygen atoms. Electrochemical characterization of RF-sputtered films was carried out by cyclic voltammetry and charge/discharge tests in the voltage range of 0.3–3.0V. Cyclic voltammetry plots showed that the RF-sputtered Co3O4 thin films were electrochemically active. X-ray photoelectron spectrometer (XPS) showed that the fresh cobalt oxide films had two peaks of Co3O4. In addition to the binding energy of cobalt oxide, the XPS spectrum of discharged film presented two additional binding energies correspond to Co metal. The first discharge capacities of as-deposited, 300, 500, and 700°C-annealed films were 722.8, 772.5, 868.4, and 1059.9μAhcm−2 μm−1, respectively. High-temperature annealing could enhance the capacity and cycle retention obviously. After 25 cycles discharging, the annealed films showed better cycle retention than as-deposited film. The 700°C-annealed film exhibited excellent discharge capacity approximated to the theoretical capacity.