The reaction of sodium salts of perfluorinated tertiary alcohols R3COH with SiCl4 provided the di‐substituted dichlorosilanes (R3CO)2SiCl2 (1 a, R=CF3; 1 b, R=C6F5), the hydrolysis of which produced the corresponding silanediols (R3CO)2Si(OH)2 (2 a, R=CF3; 2 b, R=C6F5). Unlike most other dialkoxysilanediols known in the literature, 2 a and 2 b are stable towards self‐condensation at ambient conditions. In a similar way, the related disiloxanes [(R3CO)2SiCl]2O (3 a, R=CF3) and [(R3CO)2Si(OH)]2O (4 a, R=CF3) were prepared.