Organic functional materials, including conjugated molecules and fluorescent dyes, have been intensely developed in recent years because they can be applied in many fields, such as solar cells, biosensing and bioimaging, and medical adjuvant therapy. Organic functional materials with aggregation-induced emission or aggregation-enhanced emission (AIE/AEE) characteristics have increasingly attracted attention due to their high quantum efficiency in the aggregated or solid state. A large variety of AIE/AEE materials have been designed and applied during the exponential growth of research interest in the abovementioned fields. Multiphenyl-substituted 1,3-butadiene (MPB), as a core structure that includes tetraphenyl-1,3-butadiene, hexaphenyl-1,3-butadiene and their derivatives, show a typical AIE/AEE feature and can be potentially used in all the above-mentioned fields. This review summarizes the design principles, the corresponding syntheses, and the structure-property relationships of MPBs, as well as their excellent innovative functionalities and applications. This review will be useful for scientists conducting chemistry, materials, and biomedical research in AIE/AEE-related fields.