Molecules with both aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) properties are potential organic light-emitting diode materials; however, the AIE and TADF mechanisms are still debatable. In this work, four molecules incorporating carbazole ( Cz ), phenoxazine ( PXZ ), and phenothiazine ( PTZ ) as donor groups to the diphenylsulfone acceptor were investigated. The experiment results indicate that a molecule containing Cz exhibits solely TADF properties, whereas molecules containing PXZ and PTZ demonstrate both TADF and AIE characteristics. As for DPS-PTZ , the result indicates that the thin-film environment restricts molecular twisting, consequently reducing nonradiative decay, thereby attributing to the AIE property by density functional theory and molecular dynamics simulation. As for DPS-PXZ , the result suggests that the restricted access to a conical intersection in a singlet excited via an expansion in the C-S-C angle is the pivotal factor for the AIE characteristic. The C-S-C angle twist of DPS-PXZ is impeded in the aggregate state and resulted in luminescence. Understanding the mechanisms serves as a valuable guide for the development of new AIE systems, enabling their application in various practical domains.