Abstractπ-Conjugated organic luminescent materials are essential components for modern optical and photoelectric research. This review mainly probes into the recent work in the progress of smart π-conjugated organic systems in the form of cyanostilbene and its derivatives, which can regulate its excellent features in response to a variety of physical or chemical stimuli (e.g. viscosity, light, magnetism, electric field, polarity, pH and solvent environment). As a result of its extensive applicability and adaptability, cyanostilbene and its derivatives have been planted into different structural architectures such as polymers, functional nanoparticles, solid membranes, supramolecular systems and so on. This review will first give a general description of the preparation and characterization of cyanostilbenebased optoelectric luminophores and then focus on their peculiar functional properties in the need for advanced material applications, such as AIEE (aggregation-induced enhanced emission effect), solidstate emission, photovoltaics, photolithography and photochromism to be further processed afterwards. The purpose of this review is to give a platform of practical organic materials, mostly cyanostilbene and its derivatives, based on stable aromatic derivatives, to contribute to the booming of modern π-conjugated photoelectric materials that integrate with contemporary physics, material chemistry, bioengineering, medical science and aerospace altogether.