Abstract: Azobenzene gelators AZO-1 and AZO-2 with melamine moieties were designed and synthesized with p-nitrophenol and cyanuric chloride as raw materials. Gel-sol transition temperature and critical gel concentration of AZO-1 and AZO-2 were tested. The morphologies of xerogels and photoresponsive behavior were studied by SEM and UV spectra. The results illustrated that gel-sol transition temperature of AZO-2 are higher than AZO-1 and critical gel concentration are lower. AZO-2 showed better gelation properties. The gel’s fiber aggregation structure of AZO-1 and AZO-2 were different. The fibers of AZO-1 showed good orientation and close arrangement. The fibers of AZO-2 mainly entangled to 3D network and showed cluster structure. AZO-1 and AZO-2 could also gel after irradiation of UV light. But the microstructure of the fibers changed to a certain extent. The IR spectra of gelators in different states indicated the importance of intermolecular forces in gel formation.