AbstractThe incorporation of photoswitching molecules into molecular building blocks creates the possibility of photoresponsive self‐assemblies in which the self‐assembled architecture or self‐assembling process can be controlled by external light stimulus. Among the photoswitching molecules, azobenzene has been used most widely by virtue of the large photoinduced changes in its molecular geometry and physical properties. This article reviews how azobenzene can be effectively used to construct the self‐assemblies in which supramolecular structure and formation/dissociation can be altered by light.