Twenty years ago, the concept of aggregation‐induced emission (AIE) was proposed, and this unique luminescent property has attracted scientific interest ever since. However, AIE denominates only the phenomenon, while the details of its underlying guiding principles remain to be elucidated. This mini review discusses the basic principles of AIE based on our previous mechanistic study on the photophysical behavior of 9,10‐bis( N , N ‐dialkylamino)anthracene ( BDAA ) and the corresponding mechanistic analysis by quantum chemical calculations. BDAA comprises of an anthracene core and small electron donors, which allows discussing the quantum‐chemical aspects of AIE. The key factor for AIE is the control over the non‐radiative decay (deactivation) pathway, which can be visualized by considering the conical intersection (CI) on a potential energy surface. Controlling the conical intersection (CI) on the potential energy surface enables the separate formation of fluorescent (CI:high) and non‐fluorescent (CI:low) molecules. The novelty and originality of AIE in the field of photochemistry lies in the creation of functionality by design and in the active control over deactivation pathways. Moreover, we provide a new design strategy for AIE luminogens (AIEgens) and discuss selected examples.
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