The utility of the fac‐[RuH3(PR3)3]– anion (R = Ph, C6H4‐4‐Me) for the preparation of new oligonuclear transition metal polyhydrides has been examined. The lithium salts [Li(thf)x{Ru(μ‐H)3(PPh3)3}] {1: R = Ph, x = 3; 1′: R = C6H4‐4‐Me (Tol), x = 2.5} react with [Cp*RuCl]4 (Cp* = C5Me5), ZnCl2, and CuCl(SMe2) to form new oligonuclear polyhydrido complexes. The compounds [Cp*Ru(μ‐H)3Ru(PR3)3] (2: R = Ph, 2′: R = Tol), [Zn{Ru(μ‐H)3(PPh3)3}2] (3), and [Cu2{Ru(μ‐H)3(PPh3)3}2] (4) were synthesized and characterized by multinuclear NMR and IR spectroscopy, and microanalysis. The molecular structures were determined by X‐ray crystallography. Density functional theory calculations at the PBE‐D3/def2‐TZVP level support the proposed structures of the new polyhydride complexes. The impact of intramolecular London dispersion interactions on the optimized geometries is discussed.