To investigate the effect of microstructure on the formation of the desorption peak, the volumetric thermal analysis technique (VTA) was applied to the Mg-13.5 wt% Ni hydride system. The sample made by the HCS (hydriding combustion synthesis) process had two kinds of Mg microstructures. Linear heating was started with various constant heating rates. Only one peak was appeared in the case of the small initial hydrogen wt% (0.83 wt%). Yet, two peaks were appeared with increasing initial hydrogen wt% (1.85 and 3.73 wt%) when only Mg was hydrogenated. The first peak was formed through the evolution of hydrogen from MgH2, made by eutectic Mg. The second peak was formed through the evolution of hydrogen from MgH2, made by primary Mg. Therefore, this result shows that the microstructure also has a considerable effect on forming the desorption peak. We have also derived the hydrogen desorption equations by VTA to get apparent activation energy when the rate-controlling step for the desorption of the hydrided system is the diffusion of hydrogen through the a phase and the chemical reaction B→a.