A review of experimental studies of the structure of the flame of a number of energetic materials (EMs), such as ammonium perchlorate, ammonium dinitramide, RDX, HMX, and some model composite propellants on their bases, is presented. Experimental techniques for studying the flame structure of EMs, probe mass spectrometry and the thermocouple method, are described. An analysis of experimental data on the flame structure and combustion chemistry and a comparison of them with simulations within the framework of modern mechanisms of chemical reactions in EM flames are performed.