Nano-sized W(VI)-doped TiO2 and pure TiO2 powders were synthesized successfully by hydrolysis method from precursors TiOSO4 and (NH4)6H2W12O40 with presenting urea. The prepared products were characterized by XRD, UVVIS, TEM, BET and XPS methods. Experimental results showed that the obtained W-TiO2 powders were single phase anatase, small particle size (-13-14 nm), regular particle distribution and large specific surface area (67.4 mZ/g). Moreover, the existing of W(VI) in the crystal lattice had been narrowed significantly the band gap energy of TiO2 (Eg in about 2.25-2.28 eV). Sample W-TiO2 with W/TiO2 molar ratio = 0.1 percent had the highest photo-catalytic activity. Methylene blue in aqueous solution was nearly completely decomposed after irradiation in 1 hand 1.65 times higher than TiO2 sample without doping.