The cis hydride chloride complex [(PP3)RuH(Cl)] (1) [PP3 = P(CH2CH2PPh2)3] in CH2Cl2 is capable of extracting Tl+ from TlPF6 in the aqueous phase to give [(PP3)RuH(ClTl)]PF6 (2), which contains a unique example of eta1-(Cl)-TlCl ligand. Compound 2 decomposes in refluxing THF, separating TlCl and forming the unsaturated [(PP3)RuH]+ moiety, which, by addition of PPNCl, restores the starting chloride 1 quantitatively. The latter complex is capable of transporting Tl+ from one aqueous solution through a dichloromethane solution into a second aqueous phase (U-tube experiment).