This paper presents an analysis of the observed combustion behavior of AN mixtures with different additives, fuels, and energetic materials. It has been determined on the basis of flame structure investigation by fine tungsten-rhenium thermocouples that the surface temperature of AN is controlled by the dissociation reaction of the salt occurring at the surface. Results obtained have indicated that the leading reaction of combustion of AN doped with additives proceeds in the condensed phase up to pressures of 20-30 MPa. A reason for the inability of pure AN to burn is suggested and the role of additives in the combustion mechanism is discussed.