Mechanochemically coating over-lithiated layered oxide with the multi-functional VOPO4 is studied by using that VOPO4 is capable of accommodating lithium ions that are reversibly inserted/extracted at 3.8 V vs. Li/Li+ and exerts a surface-stabilizing effect. The impregnation with VOPO4 relieves the characteristic irreversible problems of over-lithiated layered oxide, since the initial fully delithiated structure of VOPO4 provides extra lithium storage sites and thus compensates for the unavoidable loss of irreversible charging capacity of VOPO4 during the first cycle. Interestingly, VOPO4 loadings below 1 wt. % improves cycleability, whereas higher loadings result in unfavorable kinetic hindrance. Additionally, VOPO4-coated samples exhibit enhanced thermal stability due to featuring reduced decomposition exothermicity and increase thermal runaway onset temperature.