Ni-rich LiNi0.8Co0.1Mn0.1O2 oxide has been modified by ultrathin Al2O3 coatings via atomic layer deposition (ALD) at a growth rate of 1.12 Å/cycle. All characterizations results including TEM, SEM, XRD and XPS together confirm high conformality and uniformity of the resultant Al2O3 layer on the surface of LiNi0.8Co0.1Mn0.1O2 particles. Coating thickness of the Al2O3 layer is optimized at ~2 nm, corresponding to 20 ALD cycles to enhance the electrochemical performance of Ni-rich cathode materials at extended voltage ranges. As a result, 20 Al2O3 ALD-coated LiNi0.8Co0.1Mn0.1O2 cathode material can deliver an initial discharge capacity of 212.8 mAh/g, and an associated coulombic efficiency of 84.0% at 0.1 C in a broad voltage range of 2.7–4.6 V vs. Li+/Li in the first cycle, which were both higher than 198.2 mAh/g and 76.1% of the pristine LiNi0.8Co0.1Mn0.1O2 without the Al2O3 protection. Comparative differential capacity (dQ/dV) profiles and electrochemical impedance spectra (EIS) recorded in the first and 100th cycles indicated significant Al2O3 ALD coating effects on suppressing phase transitions and electrochemical polarity of the Ni-rich LiNi0.8Co0.1Mn0.1O2 core during reversible lithiation/delithiation. This work offers oxide-based surface modifications with precise thickness control at an atomic level for enhanced electrochemical performance of Ni-rich cathode materials at extended voltage ranges.