To broaden the application of aggregation‐induced emission (AIE) luminogens (AIEgens), the design of novel small‐molecular dyes that exhibit high fluorescence quantum yield ( Φ fl ) in the solid state is required. Considering that the mechanism of AIE can be rationalized based on steric avoidance of non‐radiative decay pathways, a series of bridged stilbenes was designed, and their non‐radiative decay pathways were investigated theoretically. Bridged stilbenes with short alkyl chains exhibited a strong fluorescence emission in solution and in the solid state, while bridged stilbenes with long alkyl chains exhibited AIE. Based on this theoretical prediction, we developed the bridged stilbenes BPST[7] and DPB[7] , which demonstrate excellent AIE behavior.