In summary, we synthesized a series of rhodamine-based compounds with novel crossshaped six-membered structures, namely, BISX, ISX, MISX, and MTSX, via a feasible and simple approach based on C-N and C-C coupling cyclization reaction. The compounds displayed typical AIE behavior. While different from conventional AIEgens, their AIE emission intensity did not enhance when increasing viscosity or decreasing temperature, suggesting their AIE properties were not simply attributed to the typical RIM mechanism. Combined with analysis from single-crystal structure, optical properties investigation, and theoretical calculations, we proposed that through-space interactions, resulting from aggregation-induced symmetry breaking, dominated their luminescence variations between solution and aggregation state. When dissolved in THF solutions, molecules in the ground state possessed a transition forbidden orthogonal structure with high symmetry, making it difficult to approach the transition allowed CT excited state. In the aggregate state, however, the ground-state symmetric conformation was broken due to various intermolecular interactions, affording an initial angle for realizing the transition allowed CT excited-state conformation. Besides, taking advantage of the sensitive "turnon/ off" emission behavior towards acid-base treatment, spoilage detection on seafood was realized. Therefore, aggregation-induced symmetry breaking provides a novel insight for designing unconventional AIEgens. More importantly, it offers a deep understanding of the variations between single molecular and aggregate states.