This study investigates the properties of LiCoO₂ coatings as cathodes for lithium-ion batteries, focusing on the effects of annealing on their structural, morphological, chemical, vibrational, and electrochemical characteristics. The LiCoO₂ coatings were deposited on silicon and glass substrates using RF magnetron sputtering at 100 W and subsequently annealed at 600 °C for 1 h. The films were characterized before and after annealing using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and electrochemical impedance spectroscopy (EIS). Annealing improved the crystallinity of LiCoO₂, which is critical for enhancing lithium-ion diffusion. Furthermore, an XPS analysis revealed a layered structure with a Li-rich outer layer and a Co-rich underlayer, indicating a more uniform distribution of Li and Co, along with increased oxygen content. Additionally, the annealing process refined the microstructure of the LiCoO₂ coating, positively impacting its electrochemical performance. A comparative analysis of cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) results demonstrated a significant improvement in the charge/discharge capacity post-annealing. This study successfully highlights the beneficial effects of annealing on LiCoO₂ thin-film cathodes, offering valuable insights for developing more efficient and sustainable lithium-ion batteries through sputter-deposition processes.