 Li[Li0.2Ni0.13−x+y/3Co0.13−x+y/3Mn0.54−x+y/3]AlxMoyO2 was synthesized via conventional solution combustion synthesis method. Microstructural characterizations were done by X-ray diffraction analysis and scanning electron microscopy, whereas electrochemical performance was evaluated by electrochemical tests. The electrochemical results indicated that Mo–Al doping has significant effect on capacity and cycling performance. The sample doped with Al (x = 0.015) and Mo (y = 0.015) exhibited higher cycling stability and higher capacity in comparison with those of non-substituted material. The initial discharge capacity for Mo–Al co-doped electrode was 265.5 mA h g−1 at 25 mA g−1, and capacity retention after 50 cycles was 98.2%, whilst the initial discharge capacity for bare electrode was 239.1 mA h g−1 at 25 mA g−1, and capacity retention after 50 cycles was 93%. Electrochemical impedance spectroscopy and cyclic voltammetry revealed that by the addition of Mo–Al, electrochemical performance of the Li[Li0.2Ni0.13Co0.13Mn0.54]O2 is improved.