A series of novel β-hydroxy-β-bis(trifluoromethyl)-imines (2a–j) and di(β-hydroxy-β-bis(trifluoromethyl))-diimines (3a–f) were prepared in moderate to good yields via a simple two-step approach: first, β-hydroxy-β-bis(trifluoromethyl)-ketones (1a–c) were obtained by a catalyst-free aldol reaction between liquid hexafluoroacetone sesquihydrate and ketones (acetone, acetophenone, and pinacolone, respectively); then, condensation of the latter fluorinated β-ketols 1a–c with primary amines or diamines was achieved in the presence of Lewis (montmorillonite, InBr 3 , La(OTf) 3 ) or Brönsted (PTSA) acid catalysts. The molecular structures of mono- and di-β-hydroxy-β-bis(trifluoromethyl)-(di)imines 2e,h and 3a,f were determined and found to exhibit strong intramolecular (R)N⋯H–O hydrogen bonding.