The development and application of cyclophosphazene and polyphosphazene compounds in energetic materials in recent years were classifiedly reviewed. Some synthesis and research trends of phosphazene-energetic materials were introduced. Spiro-, azide-and spiro-azide energetic cyclophosphazene compound are the three most important hazard primary explosives which have attracted more and more attention due to their excellent performance and distinctive structure characteristics. Azide-and nitric polyphosphazene will be of important significance to development environment-friendly energetic binders because of higher energy density and decomposition energy compared to conventional ones.