A detailed electronic and microstructural characterization is reported for the LiBH4–MgH2 reactive hydride composite system with and without titanium isopropoxide as additive. Surface characterization by x-ray photoelectron spectroscopy combined to a morphological study by scanning electron microscopy as well as elemental map composition analysis by energy dispersive x-ray emission are presented in this paper for the first time for all sorption steps. Although sorption reactions are not complete at the surface due to the unavoidable superficial oxidation, it has been shown that the presence of the additive is favoring the heterogeneous nucleation of the MgB2 phase. Ti-based phases appear in all the samples for the three sorption steps well dispersed and uniformly distributed in the material. Li-based phases are highly dispersed at the surface while the Mg-based ones appear, either partially covered by the Li-based phases, or forming bigger grains. Ball milling is promoting mixing of phases and a good dispersion of the additive what favors grain refinement and heterogeneous reactions at the interfaces.