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Results on studies of pure tungsten oxide WO3 and 2, 3 and 4% Fe-doped WO3 grown on the sapphire substrates by reactive pulsed laser deposition technique are reported. From X-ray diffraction it results that the crystalline structures changed with the substrate temperature and the peaks diffraction having a small shift by the amount of Fe content in WO3 lattice was noticed. Scanning electron microscopy presented a random behavior of WO3 nanocrystallites size with substrate temperatures. In the presence of 2% Fe-doped WO3, the nanocrystallites size varied gradually from 60 nm to 190 nm as substrate temperature increased. The transmission spectra of the pure and 2, 3 and 4% Fe-doped WO3 films were obtained within the 300–1200 nm spectral range. The refractive index of WO3 and Fe-doped WO3 layers were calculated by the Swanepoel method. The refractive index of pure WO3 shows a variation from 2.35–1.90 and for 2% Fe-doped WO3 from 2.30–2.00, as the substrate temperature increased. The contents of 3 and 4% Fe-doped WO3 presented nearly identical values of the refractive index with pure and 2% Fe-doped WO3, in error limits, at 600 °C. The optical band gap changes with substrate temperature from 3.2 eV to 2.9 eV for pure WO3 and has a small variation with the Fe.