We have prepared the Li-rich layered NMC composite cathode material of the composition 0.3Li(2)Mn(3)7LiMn(0.33)Ni(0.33)Co(0.33)O(2), (NMC) with 5 wt% Na doping. The latter material with composition of 0.3Li(2)MRO(3).0.7Li(0.97)Na(0.03)Mn(0.33)Ni(0.33)Co(0.33)O(2), synthesized as 200-300 nm size particles, was compared to its counterpart without Na. The discharge rate capability of the Li-rich NMC was greatly improved at both room temperature and 50 degrees C with the Na doping. The Na doped material exhibited significantly higher conductivity than its un-doped analog as evidenced by dc electronic conductivity data and impedance of Li cells. Charge/discharge cycling results Of Li cells at 50 degrees C indicated that the voltage decay of Li-rich NMC accompanied by a layer to spinel structural conversion was mitigated with Na doping. XRD analysis revealed that ionic exchange of Na occurs upon contact of the cathode material with the electrolyte and produces a volume expansion of the crystal lattice which triggers a favorable metal (probably Ni) migration to Li depleted regions during oxidation of Li2MnO3 in the first cycle. XANES data showed that Na doped NMC has better Ni reduction efficiency to provide higher rate capability. EXAFS data supported this conclusion by showing that in the case of Na doped NMC, the structure has larger crystal cage allowing for better metal migration into the Li depleted regions located in the layered unit cell of C2/m space group. XANES of Mn K-edge supported by pre-edge analysis also revealed that during charging of the electrode, the Na doped NMC was oxidized to a higher Mn valence state compared to its undoped counterpart. (C) 2013 The Electrochemical Society. All. rights reserved.