The present study sheds light on the long-standing challenges associated with high-voltage operation of LiNixMnxCo1-2xO2 cathode materials for lithium-ion batteries. Using correlated ensemble-averaged high-throughput X-ray absorption spectroscopy and spatially resolved electron microscopy and spectroscopy, here we report structural reconstruction (formation of a surface reduced layer, to transition) and chemical evolution (formation of a surface reaction layer) at the surface of LiNixMnxCo1-2xO2 particles. These are primarily responsible for the prevailing capacity fading and impedance buildup under high-voltage cycling conditions, as well as the first-cycle coulombic inefficiency. It was found that the surface reconstruction exhibits a strong anisotropic characteristic, which predominantly occurs along lithium diffusion channels. Furthermore, the surface reaction layer is composed of lithium fluoride embedded in a complex organic matrix. This work sets a refined example for the study of surface reconstruction and chemical evolution in battery materials using combined diagnostic tools at complementary length scales.