The reaction of the polyfluorinated lithium triarylmethanolates Ar₃COLi (Ar = C₆F₅, 3,5-(CF₃)₂C₆H₃) with SiCl₄ provided the monosubstituted products Ar₃COSiCl₃ (1a, Ar = C₆F₅; 1b, Ar = 3,5-(CF₃)₂C₆H₃). The hydrolysis of 1a and 1b produced the silanetriols Ar₃COSi(OH)₃ (2a, Ar = C₆F₅; 2b, Ar = 3,5-(CF₃)₂C₆H₃) without the aid of an HCl scavenger. The reaction of two equivalents of Ar₃COLi (Ar = C₆F₅, 3,5-(CF₃)₂C₆H₃) with (Cl₃Si)₂O afforded the disubstituted products [(C₆F₅)₃COSiCl₂]₂O (3a) and {[(3,5-(CF₃)₂C₆H₃)₃CO]SiCl₂}₂O (3b), the hydrolysis of which gave the corresponding disiloxanetetraols [(C₆F₅)₃COSi(OH)₂]₂O (4a) and [(3,5-(CF₃)₂C₆H₃)₃COSi(OH)₂]₂O (4b). At high concentrations in the presence of HCl, 2b undergoes controlled condensation to yield 4b. In the solid-state, 2a, 4a and 4b are mainly associated by hydrogen bonds of the type SiO–H⋯O(H)Si whereas the competing SiO–H⋯O(C)Si type was not observed.