WO3 doping and accompanying spontaneous formation of a surface phase can substantially improve the discharge capacity, rate capability, and cycling stability of Co-free Li-rich layered oxide Li1.13Ni0.3Mn0.57O2 cathode material. X-ray photoelectron spectroscopy, in conjunction with ion sputtering, shows that W segregates to the particle surfaces, decreases the surface Ni/Mn ratio, and changes the surface valence state. High-resolution transmission electron microscopy further suggests that W segregation increases surface structural disorder. The spontaneous and simultaneous changes in the surface structure, composition, and valence state represent the formation of a surface phase (complexion) as the preferred surface thermodynamic state. Consequently, the averaged discharge capacity is increased by ∼13% from 251 to 284 mAh g−1 at a low rate of C/20 and by ∼200% from 30 to 90 mAh g−1 at a high rate of 40C, in comparison with an undoped specimen processed under identical conditions. Moreover, after 100 cycles at a charge/discharge rate of 1C, the WO3 doped specimen retained a discharge capacity of 188 mAh g−1, being 27% higher than that of the undoped specimen. In a broader context, this work exemplifies an opportunity of utilizing spontaneously-formed surface phases as a scalable and cost-effective method to improve materials properties.