Li[Li1/6Ni1/6Co1/6Mn1/2]O2-xFx (x = 0.00 to 0.07) materials were synthesized with low temperature heat treatment (700 °C) and their electrochemical performances were evaluated. With the addition of fluorine, the reversible capacity significantly increased as the irreversibility was suppressed during the first cycle. The reduction of irreversibility was mainly attributed to the enhanced first cycle efficiency of Li2MnO3-like component after the fluorine addition. By combining results of the X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), In-situ X-ray absorption spectroscopy (XAS) analyses, and first principle calculations, it was proposed that the presence of fluorine facilitated the reduction of cobalt and manganese ions in Li-rich layered oxide, and that the reduced transition metal (TM) ions suppressed structural changes.