Amorphous LiFe(WO4)2 thin films have been fabricated by radio-frequency (R.F.) sputtering deposition at room temperature. The as-deposited and electrochemically cycled thin films are, respectively, characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectra techniques. An initial discharge capacity of 198mAh/g in Li/LiFe(WO4)2 cells is obtained, and the electrochemical behavior is mostly preserved in the following cycling. These results identified the electrochemical reactivity of two redox couples, Fe3+/Fe2+ and W6+/W x+ (x =4 or 5). The kinetic parameters and chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry and alternate-current (AC) impedance measurements. All-solid-state thin film lithium batteries with Li/LiPON/LiFe(WO4)2 layers are fabricated and show high capacity of 104μAh/cm2 μm in the first discharge. As-deposited LiFe(WO4)2 thin film is expected to be a promising positive electrode material for future rechargeable thin film batteries due to its large volumetric rate capacity, low-temperature fabrication and good electrode/electrolyte interface.