This study analyzed the influence of ball size and process control agents on the refinement and dehydrogenation behavior of TiH2 powder. Powders milled using ZrO2 balls with diameters of 0.1 mm, 0.3 mm, and 0.3+0.5+1 mm exhibited a bimodal particle size distribution, of which the first mode had the smallest size of 0.23 μm for the 0.3 mm balls. Using ethanol and/or stearic acid as process control agents was effective in particle refinement. Thermogravimetric analysis showed that dehydrogenation of the milled powder started at a relatively low temperature compared to the raw powder, which is interpreted to have resulted from a decrease in particle size and an increase in defects. The dehydrogenation kinetics of the TiH2 powder were evaluated by the magnitude of peak shift with heating rates using thermogravimetric analysis. The activation energy of the dehydrogenation reaction, calculated from the slope of the Kissinger plot, was measured to be 228.6 kJ/mol for the raw powder and 194.5 kJ/mol for the milled powder. TEM analysis revealed that both the milled and dehydrogenated powders showed an angular shape with a size of about 200 nm.