The reversible photoisomerization of azobenzenes has been extensively studied to construct systems with optical responsiveness; however, this process limits the luminescence of these compounds. Recently, there have been many efforts to design and synthesize fluorescent azobenzene compounds, such as inhibition of electron transfer, inducing aggregation, and metal-enhancement, which make the materials ideal for application in fluorescence probes, light-emitting devices, molecular detection, etc. Herein, we review the recently reported progress in the development of various fluorescent azobenzenes and summarize the possible mechanism of their fluorescence emission. The potential applications of these materials are also discussed. Finally, in order to guide research in this field, the existing problems and future development prospects are discussed.