The thin-film electrodes of LiNi0.8Co0.2O2 were deposited by pulsed laser ablation. The average thickness of these thin-films was measured by AFM to be approximately 0.62μm. The electrochemical properties of LiNi0.8Co0.2O2 thin-films as working electrode in lithium cells were characterized by galvanostatic charge/discharge, cyclic voltammetry and ac impedance spectroscopy. The average capacity of these thin-film electrodes is about 60–62.5μA/cm2 μm. The Li+ diffusion coefficient in the LiNi0.8Co0.2O2 thin-film electrode was measured to be in the range of 3.19×10−13–2.48×10−10 m2/s.