π-Conjugated organic luminophores are one of the essential ingredients for modern optoelectronics. This short review highlights recent research progress on a type of smart π-conjugated systems based on cyanostilbene and its derivatives, in which their photophysical properties can be tuned in response to a variety of external stimuli (e.g. polarity, viscosity, pH, light and thermal changes). To take advantage of the unique tunable features, cyanostilbene and its derivatives have been implanted into polymers, sol–gel systems, solid films, supramolecular architectures, functional nanoparticles, and so on. In addition to discussing the preparation and characterization of cyanostilbene-based hybrid materials, this review highlights their charming functionalities, such as AIEE (aggregation-induced enhanced emission) effect, solid-state emission, photochromism, photovoltaics, and biological imaging. Future studies on the applications of cyanostilbene-based intelligent materials are also predicted. The blossoming of cyanostilbene-based intelligent hybrids promises a new generation of integrated multifunctional materials, an outcome which is essential for the development of responsive materials that interface with physics, materials chemistry, biology, and medical science.