A series of dithienylethene (DTE) photoswitches with aza‐heteroaromatic cationic moieties is synthesized. The switches are characterized regarding their photochemical and photophysical properties in acetonitrile and in water. The efficiency of the switching and the photostationary state composition depend on the degree of π‐conjugation of the heteroaromatic systems. Thus, DTEs with acridinium‐derived moieties have very low quantum yields for the ring‐closing process, which is in contrast to switches with pyridinium and quinolinium moieties. All switches emit fluorescence in their open forms. The involved electronic transitions are traced back to an integrative picture including the DTE core and the cationic arms. The emission can be fine‐tuned by the π‐conjugation of the heteroaromatic cations, reaching the red spectral region for DTEs with acridinium moieties. On ring‐closing of the DTEs the fluorescence is not observable anymore. Theoretical calculations point to rather low‐lying energy levels of the highly conjugated ring‐closed DTEs, which would originate near‐infrared emission (> 1200 nm). The latter is predicted to be very weak due to the concurrent non‐radiative deactivation, according to the energy‐gap law. In essence, an ON–OFF fluorescence switching as the result of the electrocyclic ring‐closing reaction is observed.