Copper was plated on the tungsten substrate by use of a direct copper electroless plating. The optimum deposition conditions were found to be with a concentration of CuSO4 7.615 g/L, EDTA of 10.258 g/L, and glyoxylic acid of 7 g/L, respectively. The solution temperature was maintained at 60℃. The pH was varied from 11.0 to 12.8. After the deposition, the properties of the copper film were investigated with X-ray diffractometer (XRD), Field emission secondary electron microscope (FESEM), Atomic force microscope (AFM), X-ray photoelectron spectroscope (XPS), and Rutherford backscattering spectroscope (RBS). The best deposition condition was founded to be the solution pH of 11.8. In the case of 10 min deposition at the pH of 11.8, the grain shape was spherical, Cu phase was pure without impurity peak (Cu2O peak), and the surface root mean square roughness was about 11 nm. The thickness of the film turned out to be 140 nm after deposition for 12 min and the deposition rate was found to be about 12 nm/min. Increase in pH induced a formation of Cu2O phase with a long rectangular grain shape. The pH control seems to play an important role for the orientation of Cu in electroless deposition. The deposited copper concentration was 99 atomic percent according to RBS. The resulting Cu/W film yielded a good adhesive strength, because Cu/W alloy forms during electroless deposition.