In technologically important LiNi1−x−yMnxCoyO2 cathode materials, surface reconstruction from a layered to a rock-salt structure is commonly observed under a variety of operating conditions, particularly in Ni-rich compositions. This phenomenon contributes to poor high-voltage cycling performance, impeding attempts to improve the energy density by widening the potential window at which these electrodes operate. Here, using advanced nano-tomography and transmission electron microscopy techniques, we show that hierarchically structured LiNi0.4Mn0.4Co0.2O2 spherical particles, made by a simple spray pyrolysis method, exhibit local elemental segregation such that surfaces are Ni-poor and Mn-rich. The tailored surfaces result in superior resistance to surface reconstruction compared with those of conventional LiNi0.4Mn0.4Co0.2O2, as shown by soft X-ray absorption spectroscopy experiments. The improved high-voltage cycling behaviour exhibited by cells containing these cathodes demonstrates the importance of controlling LiNi1−x−yMnxCoyO2 surface chemistry for successful development of high-energy lithium ion batteries.