Sodium azide has rarely been studied in gas phase or in the form of cluster ions and as a model of solid ener-getic substances and inorganic azide salt was ionized by electrospray ionization (ESI) and studied by high resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) systematically. This paper highlights the effects of experimental conditions on the formation of salt cluster and the collision activation dissociation path-ways of cluster ions to develop a microscopic understanding of inorganic azide salt clusters. Sodium azide has rarely been studied in gas phase or in the form of cluster ions and as a model of solid energetic substances and inorganic azide salt was ionized by electrospray ionization (ESI) and studied by high resolution Fourier transform ion cyclotron resonance (FT -ICR) mass spectrometry (MS) systematically. This paper highlights the effects of experimental conditions on the formation of salt cluster and the collision activation dissociation path-ways of cluster ions to develop a microscopic understanding of inorganic azide salt clusters.