Abstract: Process for preparing alkali-metal or ammonium salts of fluorinated tertiary alcoholsRxR'y(C.sub.n F.sub.2n+1)kC--OMwherein R and R', which may be either equal to, or different from, each other, represent a perhalocarbyl group, the halogen atoms of which are constituted by F and Cl and/or Br, a hydrogenated halocarbyl group, the halogen atoms of which are constituted by F and Cl and/or Br; n is comprised within the range of from 1 to 6; M is an alkali metal or an ammonium ion; x and/or y are 0 or 1; and k is 1, 2 or 3, with the proviso that x+y+z=3, by means of the reaction of a carbonyl compoundR"--CO--R'",in which R" and/or R'"=R and/or R' or F, with a tri(alkyl)silane-perfluoroalkyl compound [(C.sub.1 -C.sub.4)-alkyl].sub.3 --Si--CnF.sub.2n+1 and with a fluoride MF, in an aprotic solvent, at a temperature comprised within the range of from -45.degree. C. to +120.degree. C.; from said salts, the corresponding alcohols can be obtained by acidic hydrolysis. Some of the obtained products are per se novel.