The Co-free layered xLi(2)MnO(3)-(1 - x)MO2(M = Mn1/3Ni1/3Fe1/3) solid solution was synthesized by a two steps approach including co-precipitation and calcination. The samples were analyzed by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron miscroscopy (SEM), dQ/dV plots and electrochemical tests. The results indicated that the material possesses a layered alpha-NaFeO2 structure with R-3m space group and exhibits excellent electrochemical performances. The initial discharge capacity is 220 mAh g(-1) in the voltage range of 2.0-4.8 V under current density of 30 mAh g(-1) at 30 degrees C, and 232 mAh g(-1) in the second discharge process. Meanwhile, the discharge capacity maintains 192.4 mAh g(-1) after 20 cycles in the voltage range of 2.0-4.8 V. Moreover, the initial discharge capacity is 263 mAh g(-1) in the cut-off voltage of 2.0-4.8 V at 50 degrees C. The high reversible capacities are attributed to reduction of Mn4+/Mn3+ during initial discharge process and the redox-reaction of Mn4+/Mn3+ during further cycles. (C) 2012 Elsevier Ltd. All rights reserved.