Intermolecular reactions of 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones (β-CCl3-β-hydroxy ketones) or 1-aryl-4,4,4-trichlorobut-2-en-1-ones (β-CCl3-enones) with nucleophiles in Brønsted superacid CF3SO3H (triflic acid, TfOH) result in various CCl3-substituted compounds in good yields. Reactions with nitriles give rise to CCl3-amides. Reactions with cyclohexane or 1,2,4,5-tetramethylbenzene as hydride ion sources afford products of ionic hydrogenation, namely, saturated CCl3-ketones. Reactions with arenes furnish arylated CCl3-ketones, which may be further cyclized into CCl3-indenes. Plausible reaction mechanisms are discussed based on DFT calculations of electronic, orbital, and electrophilic properties of the intermediate cationic species.