Three isomers of trifluoromethylphenylboronic acids were synthesized and characterized by ¹H, ¹³C, ¹¹B and ¹⁹F NMR. The investigated compounds exhibit high resistance to protodeboronation reaction. Molecular and crystal structure of these compounds was determined by single crystal XRD method. The compounds form typical hydrogen-bonded dimers with the syn-anti conformation. CF₃ substituent does not interact with boronic moiety neither as hydrogen bond acceptor nor a lone-electron pair donor. pK_a values of the isomers have been determined by spectrophotometric and potentiometric method. Introduction of the CF₃ group increases the acidity for meta and para isomers in comparison to the phenylboronic acid, while for the ortho isomer the acidity is reduced due to the steric hindrance.