This paper reports the hydrogen storage properties of a ternary hydride system, LiAlH4−MgH2−LiBH4 (molar ratio 1:1:1), both undoped and doped with TiF3 addition. It was found that there is a mutual destabilization among the three hydrides. This new ternary system possesses superior hydrogen desorption properties compared with the unary components (LiAlH4, MgH2, and LiBH4) or binary mixtures of those components (LiAlH4−MgH2, LiAlH4−LiBH4, and MgH2−LiBH4). On doping with TiF3, the system starts to release hydrogen at 60 °C and completes dehydrogenation below 400 °C. Three major dehydrogenation steps were observed in the undoped and TiF3-doped systems, which corresponds to the decomposition of LiAlH4, MgH2, and LiBH4, respectively. X-ray diffraction (XRD) measurements on the as-dehydrogenated samples were executed to identify the dehydrogenation pathway. The third step decomposition enthalpy of the doped system was determined by pressure−composition−temperature (PCT) measurements and the van’t Hoff equation ...