Dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) is a new type of nitrogen-rich ionic salt in the field of energetic materials (EMs), which has beneficial application prospects in military, aerospace, and civilian blasting fields. TKX-50 has the characteristics of easy synthesis, high energy, low sensitivity and toxicity, and good comprehensive performance and is expected to replace the traditional EMs. However, in recent years, although the physicochemical properties and application of TKX-50 have been increasing, there are no relevant comprehensive in-depth reports to discuss the existing problems and countermeasures of TKX-50. Based on the current research progress of TKX-50, this review gives a detailed overview of the synthesis, chemical and physical properties, explosive performance, safety performance, thermal decomposition behavior, catalytic modification, composite modification, and applications of TKX-50. Moreover, we summarize the application advantages and existing problems of TKX-50 and provide a prospective on the development direction and research focus in the future.