Macroporous LiNi1/3Co1/3Mn1/3O2 cathode materials were synthesized by sol-gel method with carbon spheres as the pore tuning template. The phase structure, morphology and pore nature were analyzed by X-ray diffraction, field-emission scanning electron microscopy and BET measurements. The electrochemical properties were investigated by employing cyclic voltammetry, constant current charge-discharge test, and electrochemical impedance techniques. Well developed layered structures were obtained, and removal of the carbon sphere during the calcination process led to plenty of macropores in the product, compared to the pristine dense sample without using any template. The XRD pattern showed that the structure of porous LiNi1/3Co1/3Mn1/3O2 was not affected by using the template, as which could be fully indexed to the layered structure of the a-NaFeO2 phase with crystalline size smaller than that of the pristine one. In contrast to the pristine dense sample, the templated macroporous LiNi1/3Co1/3Mn1/3O2 showed improved discharge capacity and rate capability. The specific discharge capacity of the macroporous and pristine LiNi1/3Co1/3Mn1/3O2 materials are around 189 and 155 mAh g(-1) respectively at 20 mA g(-1), and better cycling capacity retention was observed for the porous sample. The electrochemical impedance studies indicated the possible underlying mechanisms of the performance differences between the porous and pristine dense materials. These investigations indicate that the templated macroporous LiNi1/3Co1/3Mn1/3O2 might be a promising cathode material for lithium-ion battery applications. (C) 2011 Elsevier B.V. All rights reserved.