Due to the topological divergence between [3]radialene and benzene, hexaphenyl[3]radialene exhibits a dramatic bathochromic shift in emission (619 nm) with a Stokes shift >150 nm, which is distinct from its structural analogue hexaphenylbenzene. Our mechanistic analyses revealed the localized bond rearrangement and moderate short-range charge transfer, which lead to its long-wavelength emission and enhanced aggregation-induced emission character.