Prospective positive-electrode (cathode) materials for a lithium secondary battery, viz., Li[Li0.2Ni0.2−x/2Mn0.6−x/2Cr x ]O2 (x =0, 0.02, 0.04, 0.06, 0.08), were synthesized using a solid-state pyrolysis method. The structural and electrochemical properties were examined by means of X-ray diffraction, cyclic voltammetry, SEM and charge–discharge tests. The results demonstrated that the powders maintain the α-NaFeO2-type layered structure regardless of the chromium content in the range x ≤0.08. The Cr doping of x =0.04 showed improved capacity and rate capability comparing to undoped Li[Li0.2Ni0.2Mn0.6]O2. ac impedance measurement showed that Cr-doped electrode has the lower impedance value during cycling. It is considered that the higher capacity and superior rate capability of Cr-doping samples would be ascribed to the reduced resistance of the electrode during cycling.