In order to investigate the effect of LiF coating on the thermal oxidation characteristics for amorphous boron powder, the thermal analysis experiment of boron coated with LiF (B^LiF) was conducted by DSC-TG. Propellant samples containing B^LiF were prepared. The heat of detonation and heat of combustion were determined by an oxygen bomb calorimeter. The effects of B^LiF on the energy release features in primary combustion and after-burning processes of the propellant were discussed. The results indicate that in comparison with amorphous boron, B^LiF shows a fast oxidation reaction at 599 ℃, and a 39.9% higher percentage of boron participated in B/O reaction. The propellant containing B^LiF makes primary combustion and after-burning energy release efficiencies (η_c1 and η_c2) increased and combustion efficiencies of B enhanced significantly from 65.48% to 81.57%. This is due to the consumption of B₂O₃ layer on the boron particle surface via endothermic reaction of LiF and B₂O₃ at high temperature and the acceleration of B/O reaction.