Abstract: The self-assembly of π-conjugated molecules have provided an attractive platform for the development of novel organic functional materials because of their excellent photoelectronic properties. This review has mainly reviewed the recent research progress of self-assembled nanoaggregates and gels as well as their applications to construct organic supramolecular functional and smart materials based on α-cyanostilbene and their derivatives. The general structural features of α-cyanostilbene have been overviewed, then the strong luminescence, chiroptical properties and nano-organization controllability of α-cyanostilbene supramolecular nanostructures as well as the multistimuli responsiveness in gel system were highlighted. Specially, the photoreactions of α-cyanostilbene and the featured work of the photoreactions utilized into self-assembly system were also reviewed. Finally, our relevant work in this field were introduced.