The ruthenio-hydridosilanes C 5 Me 5 (OC) 2 Ru-SiR 2 H [R = Me (3a), o-Tol (3b)] are accessible from the metallating reagent K[Ru(CO) 2 C 5 Me 5 ] (1a) and the corresponding chlorosilanes R 2 SiHCl (2a,b). Similarly obtained Cp(OC) 2 Ru-Si(H)(p-Tol)Cl (3c) is converted to the ruthenio-dihydridosilane Cp(OC) 2 Ru-Si(p-Tol)H 2 (4) with LiAlH 4 . Oxofunctionalization of 3a,b and 4 with dimethyldioxirane affords the novel ruthenio-silanols C 5 Me 5 (OC) 2 Ru-SiR 2 OH [R = Me (6a),o -Tol (6b)] and Cp(OC) 2 Ru-Si(p-Tol)(OH) 2 (7). Compound 6b undergoes condensation with Me 2 Si(H)Cl (2a) to yield the ruthenio-disiloxane C 5 Me 5 (OC) 2 Ru-Si(o-Tol) 2 OSiMe 2 H (8). The structure of 6b, established by X-ray analysis, reveals the formation of discrete units linked by one hydrogen bond.