Lithium-rich layered oxides are recognized as promising materials for Li-ion batteries, owing to higher capacity than the currently available commercialized cathode, for their lower cost. However, their voltage decay and cycling instability during the charge/discharge process are problems that need to be solved before their practical application can be envisioned. These problems are mainly associated with a phase transition of the surface layer from the layered structure to the spinel structure. In this paper, we report the AlF 3-coating of the Li-rich Co-free layered Li 1.2 Ni 0.2 Mn 0.6 O 2 (LLNMO) oxide as an effective strategy to solve these problems. The samples were synthesized via the hydrothermal route that insures a very good crystallization in the layered structure, probed by XRD, energy-dispersive X-ray (EDX) spectroscopy, and Raman spectroscopy. The hydrothermally synthesized samples before and after AlF 3 coating are well crystallized in the layered structure with particle sizes of about 180 nm (crystallites of~65 nm), with high porosity (pore size 5 nm) determined by Brunauer-Emmett-Teller (BET) specific surface area method. Subsequent improvements in discharge capacity are obtained with a~5-nm thick coating layer. AlF 3-coated Li 1.2 Ni 0.2 Mn 0.6 O 2 delivers a capacity of 248 mAh g −1 stable over the 100 cycles, and it exhibits a voltage fading rate of 1.40 mV per cycle. According to the analysis from galvanostatic charge-discharge and electrochemical impedance spectroscopy, the electrochemical performance enhancement is discussed and compared with literature data. Post-mortem analysis confirms that the AlF 3 coating is a very efficient surface modification to improve the stability of the layered phase of the Li-rich material, at the origin of the significant improvement of the electrochemical properties.