The fluorinated trityl alcohols (C6F5)3COH, (C6H2F3)3COH and (C6(CF3)2H3)3COH were prepared in good to excellent yields by a facile one‐step procedure. These alcohols and their lithium salts were fully characterized by NMR and IR spectroscopy, mass spectrometry and XRD analysis. The molecular structures reveal that the differences in the fluorination patterns result in a divergent coordination behavior in their lithium salts. Experimental and computational studies concerning the acidity show similar electron withdrawing character of the substituents and disclose acidity properties in the range of phenols.