Porous LiNi 1/3 Co 1/3 Mn 1/3 O 2 microspheres were synthesized by a co-precipitation approach combined with high-temperature calcination. To improve the electrochemical performances, phosphate coating was formed on the surfaces of porous LiNi 1/3 Co 1/3 Mn 1/3 O 2 microspheres by H 3 PO 4 etching and subsequent annealing treatment. As anticipated, phosphate-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 microspheres (2mol.% H 3 PO 4 ) delivered discharge capacity of 100. 1mAhg −1 at 5°C, which was higher than that of pristine LiNi 1/3 Co 1/3 Mn 1/3 O 2 microspheres (64.8mAhg −1 ). The improvement of rate capability and cycle stability of LiNi 1/3 Co 1/3 Mn 1/3 O 2 microspheres could be attributed to the phosphate coating, which suppressed the side reaction between cathode and electrolyte. The phosphate surface modification has a promising application in improving the performance of layered oxide cathode materials for lithium ion batteries.