Lithium borohydride (LiBH4) has gained extensive attention as potential hydrogen storage media, however, high thermodynamic stability, slow kinetics, and limited reversibility are still major hurdles. In this paper, high-dispersed MgF2@C was successfully synthesized via carbonization process at high temperature, and a series of work have been taken for the influences of MgF2 and MgF2@C on LiBH4. Microstructure analyses reveal that the MgF2 could cause F, and then accelerate the thermodynamic instability for LiBH4, therefore, improving the hydrogen storage property. This fundamental understanding provides us with that the exist of carbon skeleton could prevent the aggregation of the composite or separation for the additive in the de/hydrogenation process at high temperature, and the high-dispersed MgF2 could provide more reactive sites, which greatly increase the dissociation and restructuring for H2, improving the catalytic efficiency. Temperature programmed desorption (TPD) analyses show that MgF2@C could reduce the onset temperature and the peak temperature for 100 ?C and 86 ?C, respectively, and the final hydrogen desorption capacity reaches 6.58 wt.%, indicating that the addition of MgF2@C is not significantly reduce the hydrogen capacity. In the process of isothermal hydrogen desorption, the rate of LiBH4-MgF2@C composite is three times of LiBH4-MgF2@C.