In this work we prepared Li1.2Ni0.2Mn0.6O2 (LNMO) using a hydroxide co-precipitation method and investigated the effect of co-modification with NH4F and Al2O3. After surface co-modification, the first cycle coulombic efficiency of Li1.2Ni0.2Mn0.6O2 improved from 82.7% to 87.5%, and the reversible discharge capacity improved from 253 mAh g-1 to 287 mAh g-1 at C/20. Moreover, the rate capability also increased significantly. A combination of neutron diffraction (ND), high-resolution transmission electron microscopy (HRTEM), aberration-corrected scanning transmission electron microscopy (a-STEM) / electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS) revealed the changes of surface structure and chemistry after NH4F and Al2O3 surface co-modification while the bulk properties showed relatively no changes. These complex changes on the material’s surface include the formation of an amorphous Al2O3 coating, the transformation of layered material to a spinel-like phase on the surface, the formation of nanoislands of active material, and the partial chemical reduction of surface Mn4+. Such enhanced discharge capacity of the modified material can be primary assigned to three aspects: decreased irreversible oxygen loss, the activation of cathode material was facilitated with pre-activated Mn3+ on the surface, and stabilization of the Ni redox pair. These insights will provide guidance for the surface modification in high voltage cathode battery materials of the future.