Porous LiNi1/3Co1/3Mn1/3O2 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 LiNi1/3Co1/3Mn1/3O2 microspheres by H3PO4 etching and subsequent annealing treatment. As anticipated, phosphate-coated LiNi1/3Co1/3Mn1/3O2 microspheres (2mol.% H3PO4) delivered discharge capacity of 100. 1mAhg−1 at 5°C, which was higher than that of pristine LiNi1/3Co1/3Mn1/3O2 microspheres (64.8mAhg−1). The improvement of rate capability and cycle stability of LiNi1/3Co1/3Mn1/3O2 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.