Combustion of energetic materials (EMs) with the leading reaction in the condensed phase is considered. It is assumed that the leading role belongs to the condensed phase not only when the heat flux from the gas to the burning surface is negligibly small, but also in the case of a substantial heat flux, which is consumed for evaporation of unreacted substance. Based on numerous thermocouple-aided experimental studies on combustion of different EMs, it has been shown that the condensed phase can be heated up to its maximum temperature-boiling point-or, in the case of onium salts, dissociation temperature. A microscopic equilibrium at the surface between the boiling substance and vapor rather than a macroscopic one has been supposed to exist that is responsible for the observed surface temperatures. Combustion of AP, ADN, HMX, RDX, and CL-20 is considered here, and resulting kinetic parameters of the leading reactions have been derived from experimental data on the burning rates and surface temperatures, provided burning of these materials follow the condensed-phase combustion model. Using kinetic parameters of the leading reaction and the dependence of the surface temperature on pressure, burning rates of EMs have been simulated in a wide interval of initial temperature and pressure. © 2010 by Begell House, Inc.