Nanoscale tungsten (W) powder is used in some special materials. In this study, a hollow superstructure W powder consisting of nanoparticles was synthesized by spray drying combined with two-step calcination from commercial (NH4)6W7O24·6H2O. The high-pressure gas (HPG) was the significant factor in spray drying process, which affect the BET surface area and average particles size of the spray-dried powders. The detailed influences of calcined steps and calcination temperature in the microstructure and average particles size of final W particles were investigated. The size distribution of as-synthesized nanoscale W particles with hollow superstructure was from 40 to 200 nm, and the average size was about 100 nm. The as-synthesized W powder shows good sintering properties. It should be noted that the powder technology in this study can be used to synthesize other powders with high-performance requirements. .