The coordination properties of ortho- and meta-substituted [(2-diphenylphosphanylethyl)phenyl]methanol 4a and 4b toward ruthenium(II) have been investigated. To ensure coordination of both the arene and the tethered phosphine, the labile ruthenium arene dimer [RuCl2(EtO2CC6H5)]2 (7) was synthesized and structurally characterized. Both the ortho and meta isomers [Ru(4a)Cl2] (9a) and [Ru(4b)Cl2] (9b) were characterized by X-ray crystallography. The lack of reactivity of the benzylic alcohol functionality in complexes 9a and 9b toward various P and C electrophiles is rationalized with extended Hückel calculations.