Abstract : On page 1410, a new gated photochromism and fluorescence switches are successfully achieved in a ferrocene‐modified diarylethene system with a sterically hindered ethene bridge. The photoinactive parallel conformer and photoactive antiparallel conformer are individually investigated by W.‐H. Zhu and co‐workers. The different conformers show redox‐gated photochromism and reversible redox reactions can also switch the fluorescence of the naphthalimide chromophore "ON" and "OFF".