The use of metal powder as fuel in high-energy materials (HEM) for propulsion is the most energy-efficient method to increase the burning rate, combustion temperature, and specific impulse. Typically, various dispersity aluminum powders are used in the HEM composition. To improve the ignition and combustion characteristics of the HEM composition it is advisable to use the catalysts (nonmetals, metals or their oxides). This paper presents the experimental data of the HEM samples ignition containing ammonium perchlorate, butadiene rubber, micron powders of aluminum, aluminum-magnesium alloy, as well as nanopowders of amorphous boron, aluminum-copper, and aluminum-boron mixtures. The use of aluminum-copper or aluminum-boron nanopowders in the HEM composition decreases the ignition delay time by 1.3–2.0 times in comparison with Al-based HEM during CO2 laser initiation. In the case of Al-Mg powder use, the ignition delay time is changed slightly.