Ni-coated tungsten powder was prepared by liquid-solid doping method combined with air calcination and hydrogen reduction method. The nickel doping process in WO3 and its effect on the reduction behavior of tungsten oxide were studied. The results show that after calcination, most of the Ni ions will occupy the lattice positions of the main W ions and reduce the interplanar spacing of WO3. The latter is due to the promotion of the generation of oxygen vacancies in WO3 rather than the change of ionic radius. After hydrogen reduction, the doped Ni atoms precipitate on the surface of the W particles in the form of a thin metal coating. Therefore, as the amount of Ni added increases, the size and morphology of the reduced W particles change greatly. By using first-principles calculations, it is also found that the presence of Ni reduces the reduction barrier of WO3. Finally, W-Ni compacts were sintered at 1500°C in a hydrogen atmosphere, and the accelerated densification of W alloys after Ni doping was discussed.