Poor rate capability and capacity degradation of LiNixCoyMnzO2 restricts its practical commercial applications at high operating voltage (>4.3 V). LiNi1/3Co1/3Mn1/3O2 is successfully modified by tungsten compound through a cost-effective ball-milling and annealing process. The rate capability of W-modified cathode is increased by 57.6% at 10C in 3.0–4.5 V. Moreover, after 100 cycles the capacity retention is improved from 80% to 96% under 0.5C. At 1C, W-modified cathode still maintains 145 mAh g−1 discharge capacity after 100 cycles, which has 16% increase than pristine LiNi1/3Co1/3Mn1/3O2. The improvements on rate and cycle performance are introduced by enhanced Li-ion diffusion and surface stability by tungsten modification.