This paper presents the results of a series of experiments on the condensed phase decomposition and the gas phase combustion of hydrazinium nitroformate (HNF). The experiments include SEM analysis of quenched samples that showed evidence of the formation of a foam layer. FTIR spectrometry and mass spectrometry provide details on species formation during decomposition and combustion. The analysis of the results led to the identification of probable overall reactions in the low pressure regime around 0.1 Mpa. It is found that decomposition of HNF takes place through formation of ammonium nitroformate, and through dissociative vaporisation. The gas phase near the surface of burning HNF is expected to contain a large amount of hydrazine, ammonia and nitrogen dioxide (as a decomposition product of nitroform). The primary reaction zone of the HNF flame is then associated with the exothermic reactions of these species. The resulting nitrogen oxide is subsequently reduced to molecular nitrogen in the secondary flame. (C) 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.