The gas-phase acidities of 1-adamantanol and perfluoro1-adamantanol were determined by means of Fourier transform ion cyclotron resonance spectrometry (FT-ICR). The acidity of perfluoro1-adamantanol seems to be the highest ever reported for an alcohol. A computational study of these species and their anions at both the MP2/6-311+G(d,p) and B3LYP/6-311+G(d,p) levels was performed. Also studied were the tertiary alcohols (including their perfluorinated forms) derived from norbornane, bicyclo[2.2.2]octane and cubane. It was found that: (i) the intrinsic acidity of non-fluorinated bridgehead alcohols increases with the strain of the hydrocarbon framework and, (ii) perfluorination of these compounds strongly increases their acidity and, likely, significantly modifies their internal strain.