The demand for high-performance lithium-ion batteries and thus efficient cathode materials is steadily increasing. In addition to a high energy density and long lifetime, these should also be cost-effective and environmentally benign. Manganese-based materials have particular potential because manganese is available in sufficient quantities and can be supplied at a comparatively low cost. Hence, in this study, manganese-based disordered rock salt oxyfluorides Li2Mn1–xVxO2F (0 ≤ x ≤ 0.5) are synthesized as cathode materials for lithium-ion batteries using high-energy mechanochemical ball-milling. The effect of partial vanadium substitution on the sample properties is analyzed, focusing on the electrochemical properties. Furthermore, a heat treatment process for stabilization of the samples is followed, where the morphology and structure of the samples are studied by powder X-ray diffraction and electron microscopy (SEM/TEM). The oxidation states of the transition metals in the synthesized compositions are further investigated using X-ray absorption near-edge structure spectroscopy. The data analysis reveals that the heat treatment resulted in increased symmetry and reduced defects of ball-milled compounds, but it may also affect the local fluorination degree in the structure. However, the results show that this treatment process has a beneficial effect on capacity retention of the formulated electrodes (∼81% after 100 cycles), a faster response to the change of cycling rate, and less increase in charge-transfer resistance of the samples during cycling. Such a structural improvement attributed to mitigation of the surface/bulk defects is an additional input to the series of cathode candidates of low temperature stability.