Heat of formation is an important thermochemical parameter, which determines the combustion and. detonation performances of energetic materials and nitrogen-rich compounds can be considered as high-performance energetic materials. A novel method is introduced to predict the heats of formation of high nitrogen content materials (N > 50%) including different derivatives of triazble, tetrazole, triazine, tetrazine, furazan, and some of organic nitrogen-containing chains. It is based on elemental composition and some of the molecular moieties, such as azido, azo, azoxy, guanidino, carbonyl, hydroxide and amino groups. High reliability of the new model has been proved in comparison with two recent quantitative structure-property relationships (QSPR) and group additivity methods as well as different quantum mechanical approaches. For 96 high nitrogen content compounds, the values of standard deviation (SD) are 61.6, 131.1 and 110.1 kJ/mol for the new method, QSPR method and group additivity method. The values of SD are 92.8 and 103.3 kJ/mol for the new and quantum mechanical methods, respectively, where the calculated data of different quantum mechanical approaches were available. (C) 2016 Elsevier B.V. All rights reserved.