A new tris-heteroleptic complex [Ru(bpy)(dppz)(OSO)](ClO4), [1](ClO4) (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine and OSO = 2-methylsulfinylbenzoate), was synthesized and characterized to control the photochromic Ru-S -> Ru-O linkage isomerization. Details isomerization kinetics studied by UVvisible absorption spectroscopy and cyclic voltammetry revealed that efficient photochromic S -> O isomerization and thermal O -> S reversal take place in solvents like propylene carbonate (PC), methanol, and dichloromethane. Strikingly, photoisomerization of [1](ClO4) is arrested in water although is active in the analogous compound [Ru(bpy)(2)(OSO)](ClO4). Effective excited state deactivation through dark 3MLCT state involving dppz ligand of [1](ClO4) switches off photochromism in aqueous medium. Interestingly, the photochromism is activated in aqueous solution in the presence of DNA which shields the dppz localized dark state through intercalation. Ultrafast transient absorption spectroscopic measurement sheds light on the differential behavior of photochromism in aqueous and nonaqueous solvents.