Among some promising candidates for high-capacity energy and hydrogen storage is the Lithium-Boron Reactive Hydride Composite System (Li-RHC: 2 LiH + MgB2/2 LiBH4 + MgH2). This system desorbs hydrogen only at relatively high temperatures and presents a two-step series of reactions occurring in different time scales: first, MgH2 desorbs, followed by LiBH4. Hitherto, the dehydrogenation kinetic behavior of such a system has been described for different temperatures at specific values of operative pressure. However, a comprehensive model representing its dehydrogenation kinetic behavior under different operative conditions has not yet been developed. Herein, the separable variable method is applied to develop a comprehensive kinetic model, including the two-step dehydrogenation series reaction. The MgH2 decomposition is described with the one-dimensional interface-controlled reaction rate Johnson-Mehl-Avrami-Erofeyev-Kholmogorov (JMAEK) with a (Pequilibrium/Poperative) pressure functionality and an Arrhenius temperature dependence activation energy of 63 ± 3 kJ/mol H2. The LiBH4 decomposition is modeled applying the autocatalytic Prout-Tompkins model. A novel approach to describe the Prout-Tompkins t0 parameter as a function of the operative temperature and pressure model is proposed. This second reaction step presented a (Pequilibrium – Poperative/Pequilibrium)2 pressure dependence and an Arrhenius temperature dependence with activation energy 94 ± 13 kJ/mol H2. The proposed approach is experimentally and computationally validated, successfully describing the decomposition kinetic behavior of MgH2 and LiBH4 under three-phase gas, liquid and solid environment and shows good agreement between experimental and modeled curves.