Lithium metal anodes have long been considered as "holy grail" in the field of energy storage batteries, but dendrite growth and large volume changes hinder their practical applications. Herein, a facile and eco-friendly CF 4 plasma treatment is employed for the surface modification of Li anodes, and an artificial layer consisting of LiF and Li 2 C 2 is fabricated for the first time. Experimental results and theoretical calculations reveal that the high adsorption energy of LiF and low Li + diffusion barriers in Li 2 C 2 induce uniform nucleation and planar growth of Li, guaranteeing a stable and dendrite-free Li structure during the repeated plating/stripping process of cycling. Symmetric cells using CF 4 plasma-treated Li operate stably for more than 6500 h (at 2 mA cm −2 and 1 mAh cm −2 ) or 950 h (at 1 mA cm −2 and 10 mAh cm −2 ). When paired with a LiFePO 4 cathode, full batteries deliver a high reversible capacity of 136 mAh g −1 (at 1 C) with considerable cycling stability (97.2% capacity retention over 200 cycles) and rate performance (116 mAh g −1 up to 5 C). This powerful application of plasma technology toward novel LiF-Li 2 C 2 artificial layers provide new routes for constructing environment-friendly and high-performance energy storage devices.