The paper presents the results of thermodynamic calculations of the effect of pure boron additives on combustion characteristics of high-energy materials (HEM) based on ammonium perchlorate, ammonium nitrate, active fuel-binder, and powders of aluminum Al, titanium Ti, magnesium Mg, and boron B. The combustion parameters and the equilibrium composition of condensed combustion products (CCPs) of HEM model compositions were obtained with thermodynamic calculation program “Terra.” The compositions of solid propellants with different ratios of metals (Al/B, Ti/B, Mg/B, and Al/Mg/B) were considered. The combustion temperature Tad in a combustion chamber, the vacuum specific impulse J at the nozzle exit, and the mass fraction ma of the CCPs for HEMs were determined.