Crystalline CuF2 thin films were prepared by pulsed laser deposition under room temperature. The physical and electrochemical properties of the as-deposited thin films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic cycling and cyclic voltammetry (CV). Reversible capacity of 544mAhg−1 was achieved in the potential range of 1.0–4.0V. A reversible couple of redox peaks at 3.0V and 3.7V was firstly observed. By using ex situ XRD and TEM techniques, an insertion process followed by a fully conversion reaction to Cu and LiF was revealed in the lithium electrochemical reaction of CuF2 thin film electrode. The reversible insertion reaction above 2.8V could provide a capacity of about 125mAhg−1, which makes CuF2 a potential cathode material for rechargeable lithium batteries.