Abstract: | Typically, molecules with a twisted donor–acceptor (D‐A) architecture have been exploited for constructing thermally activated delayed fluorescence (TADF) materials. Herein, we report the first example of a thiophene‐based thermally activated delayed fluorescent molecule without a D‐A architecture. Compound 1 (2,5‐bis(2,2‐di(thiophen‐2‐yl)vinyl)thiophene) is conformationally flexible and shows weak fluorescence in the solution state but displays bright TADFin both condensed and solid states. Compound 1 crystallized in two different polymorphs ( 1 a and 1 b ). Interestingly, both polymorphs show distinctly different TADF features. The broad spectral features and the TADF characteristics of 1 have been explored for the time‐dependent multicolor (green, yellow and red) imaging of living cells. |