In light of the extensive use of tungsten (W) in fusion experimental devices and the importance of hydrogen isotopes permeation, based on the first principle approaches we study the effects of W doping on the formation energies of intrinsic point defects, hydrogen interactions with such defects, and hydrogen diffusion in bulk of α-Al2O3. Our investigation demonstrated that W doping enhances the formation of oxygen and aluminum vacancies (Vo and VAl) in α-Al2O3. In W doping α-Al2O3, hydrogen primarily exists in the form of Ho− (hydrogenation of the bulk VO3−) and Hi− (H interstitial) defects, while it hardly occupies VAl. Hydrogen is firmly trapped by Vo with a formation energy −3.35eV, and Hi− diffusion become extremely challenging because W doping significantly raises the Hi− diffusion barrier to 4.44 eV. Our findings indicate that W doping is beneficial for hydrogen permeation resistance in α-Al2O3.