The effects of the heat treatment temperature and of the atmosphere on the dehydrogenation and hydrogen reduction of ball-milled TiH2-WO3 powder mixtures are investigated for the synthesis of Ti-W powders with controlled microstructure. Homogeneously mixed powders with refined TiH2 particles are successfully prepared by ball milling for 24 h. X-ray diffraction (XRD) analyses show that the powder mixture heat-treated in Ar atmosphere is composed of Ti, Ti2O, and W phases, regardless of the heat treatment temperature. However, XRD results for the powder mixture, heat-treated at 600oC in a hydrogen atmosphere, show TiH2 and TiH peaks as well as reaction phase peaks of Ti oxides and W, while the powder mixture heat-treated at 900oC exhibits only XRD peaks attributed to Ti oxides and W. The formation behavior of the reaction phases that are dependent on the heat treatment temperature and on the atmosphere is explained by thermodynamic considerations for the dehydrogenation reaction of TiH2, the hydrogen reduction of WO3 and the partial oxidation of dehydrogenated Ti.