Cationic diarylethenes with an imidazolium ring are synthesized for the first time. The imidazolium cationic moiety is connected directly to the ethene unit as one of the aryl units that take part in the photoinduced pericyclization reaction. The imidazolium-substituted diarylethenes undergo reversible photochromic reactions in a variety of organic media, including ionic liquids, even though they have a delocalized cationic charge in one of the five-membered aromatic rings. The closed-ring isomer shows solvatochromism depending on the solvent donor numbers. Addition of some tetraalkylammonium salts, such as tetrabutyl ammonium nitrate, into the colored organic solution of diarylethene also causes a color change, indicating its ionochromic property. These solvato- and ionochromic properties are considered in connection with the shift of chemical equilibrium between the closed-ring isomers, one with an extended pi-conjugation system and one with limited pi-conjugation due to the strong interaction with solvent molecules and anions with high donor number.