Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and, lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a "reaction in the beaker", avoiding direct handling of highly toxic fluorine gas. For lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes: the reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm(2). Lithiated silicon can serve as either a pre-lithiation additive, for existing lithium-ion batteries or-a replacement for lithium metal in Li-O-2, and Li-S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent,N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection-of crystalline and dense LiF coating, LixSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows LixSi to be stable in humid air (similar to 40% relative humidity). Therefore; this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.