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Boron and its compounds are considered as possible high efficiency fuel components for high-energy materials (HEMs), since they have high gravimetric and volumetric heats of oxidation in comparison with aluminium powder. This work aims to modify a commercial 99.5% pure boron and AlB2 or TiB2 powders to improve the ignition and combustion characteristics for solid propellants. The ignition parameters for the model HEM sample based on ammonium perchlorate, ammonium nitrate and energetic binder, containing Al, B, AlB2 and TiB2 powders are presented. It was found that the greatest effect at the laser ignition is achieved at a full replacement of Al by B powder, at which the ignition time and the activation energy of HEM are reduced by 2.1–2.7 and 1.8 times, respectively. When replacing Al by AlB2 powder in HEM the ignition time is reduced by 1.7–2.4 times, and the activation energy is increased by 1.4 times.