This paper presents a new approach to predict the condensed phase heat of formation in important classes of energetic compounds including acyclic and cyclic nitramines, nitrate esters and nitroaliphatics. The condensed phase heat of formation has been expressed by a combination of a core heat of formation, which is a function of elemental composition of the energetic compound, and correction functions. The correction functions for some energetic compounds can have decreasing or increasing effects on the basis of thermodynamic stability. It has been shown that this model can offer reliable predictions for the above energetic compounds compared to the calculated outputs of the best recent empirical and complex quantum mechanical methods. (C) 2009 Elsevier B.V. All rights reserved.