The cubic sodium tungsten bronzes, NaxWO3(x=0.854 and 0.814)were prepared by rare earths gaseous permeation method. Structural analysis was carried out by Rietveld method from powder X-ray diffraction data. The X-ray diffraction profile calculated with cubic P32 models are in good agreement with the observed X-ray diffraction patterns. There is only a little difference in W-O bond and Na-O bond between Na0.854WO3 and Na0.814WO3. Conductivity measurements indicate that NaxWO3 show anomalous semiconducting behavior and percolation model was used to interpret it.