Emerging demands to develop simple, low-cost, and handy chemical sensors for diverse real-world applications are noteworthy. To attain all such needs, highly sensitive fluorescence (FL)-based detection has arisen as a promising and powerful technique since the 1980s. The fascinating growth of diverse FL-based molecular systems for chemosensing has offered a new branch in analytical chemistry. Despite introducing various emissive small molecules, polymers, and metal/covalent organic frameworks (MOF/COF), progress in implementing fluorescence-based devices for on-site applications is challenging. The lack of substantial emission in the conventional probes’ aggregate/condensed/solid state and constructing emissive supramolecular material is the crucial bottleneck to introducing a suitable chemosensing device. Furthermore, finding a competitive media for chemosensing is also a significant concern. The pioneering discovery of AIE-active materials has offered a revolution in chemosensing by resolving the weak points of typical fluorophores. The emerging AIE feature has offered deeply emissive supramolecular materials for various essential analytes in the health, environment, food, and national security sectors. Herein, this compendium aims to provide critical benefits and the underlying causes of picking supramolecular AIE-active luminogens (AIEgens) as chemosensing probes compared to conventional fluorophores. Scientific understanding is essential for designing efficient AIE-active supramolecular materials for chemosensing. With such consideration, the competence and sensing mechanism of various supramolecular AIE-active materials-based detection strategies of essential analytes of worldwide concern will be delineated.