The Cu/ZrW2O8 gradient films have been deposited on silicon substrates by RF magnetron sputtering with copper and compound targets followed by annealing in argon atmosphere at 750 °C for 3 min. The three different compound targets were B1 (nZrO2:nWO3=1:2.2), B2 (nZrO2:nWO3=1:2.5) and B3 (ZrW2O8), respectively. The as-deposited gradient films were amorphous, while a post-deposition annealing at elevated temperature was required for the development of the cubic ZrW2O8. The structure and surface morphology of the gradient films were then studied using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectrometer (EDS). The globular and slender rod crystals can be found in annealed films, which are copper and ZrW2O8, respectively. The fine gradient film should be obtained using the target B1.