The novel donor-acceptor-donor (D-A-D)-type fluorophore with an asymmetric structure is reported. The twisted-induced charge transfer (TICT) luminescence was observed. The degree of charge transfer and radiative rate constant in the luminescence increased simultaneously with increase in orientational polarizability of solvents. In contrast to the numerous CT fluorophore researches, this behavior has never been previously observed. This characteristic behavior reveals the existence of an effective exciton coupling between the CT states in the donor-acceptor-donor-type fluorophore for the first time.

An asymmetric donor–acceptor–donor (D–A–D) type organic luminophore is reported for solvent and temperature sensors. The electronic absorption and luminescence properties of the luminophore were assessed from its electronic absorption and luminescence spectra, which depended on the external environment. The D–A–D luminophore showed environment‐sensitive charge transfer fluorescence based on structural transformation through excited singlet states. Characteristic D–A–D phosphorescence was also observed at 494 nm, which was shorter than that of the D–A–D fluorescence (502 nm). In this study, the novel photophysical properties of a D–A–D‐type luminophore induced by its asymmetric electronic structure are described.