Ruthenium(II)-arene diphosphine complexes are shown to be effective precursors for the catalytic hydrogenation of the C=C bond in an aqueous biphase using molecular hydrogen as the hydrogen source. A mechanistic study performed in water, utilizing high gas pressure NMR spectroscopy and electrospray ionization mass spectrometry, and experiments involving the variation of pH, enables indirect identification of the catalytically active species resulting from the substitution of the chloride with the dihydrogen ligand. Similar catalytic experiments are carried out in ionic liquids (ILs), such as [bmim][BF4] and [bmim][TfO] using an analogous precursor, but no conversion is observed and the ruthenium(II) species does not undergo any chemical change during the reaction. The dissociation of chloride, leading to the catalyst, is inhibited in these ILs due to a lower solvation of chloride. An estimate of the bmim-chloride interaction, which is lower than the water-chloride interaction, is determined by 1H NMR spectroscopy. To ensure the formation of the active species in such ILs, the coordinated chloride is abstracted beforehand and replaced by acetonitrile, which restores the catalytic activity. An alternative approach to overcome the chloride dissociation problem consists of improving the solvation of the chloride in the IL medium. To accomplish this, water is added as a co-solvent in the IL phase and, under these conditions, the activity is restored. In order to assess the reactivity of chloride ions in ILs, a relative scale for the solvation of chloride is given for a series of [cation][Tf2N] ILs. This scale, based on the reaction enthalpy for the dissociation of a chloride-templated metallacage, yields the following order of chloride solvation: [C5e3am][Tf2N] < [bmpy][Tf2N] < [bmim][Tf2N] ≤ [bdmim][Tf2N] < [bpy] [Tf2N] ≪ [mimeOH][Tf2N]. In Tf2N-based ILs, the catalytic activity of hydrogenation reactions using the same Ru(II) precursor in the presence of chloride is totally modified. In a series of [cation][Tf2N] ILs, the rate of formation of the catalyst, which is promoted by chlorides, is shown to depend on the solvation of chloride.