Organoboranes carrying electron-withdrawing substituents are commonly used as Lewis acidic catalysts or cocatalysts in a variety of organic processes. These Lewis acids also became popular through their application in `frustrated Lewis pairs',i.e.combinations of Lewis acids and bases that are unable to fully neutralize each other due to steric or electronic effects. We have determined the crystal and molecular structures of four heteroleptic arylboranes carrying 2-(trifluoromethyl)phenyl, 2,6-bis(trifluoromethyl)phenyl, 3,5-bis(trifluoromethyl)phenyl or mesityl substituents. [3,5-Bis(trifluoromethyl)phenyl]bis[2-(trifluoromethyl)phenyl]borane, C22H11BF12, (I), crystallizes with two molecules in the asymmetric unit which show very similar geometric parameters. In one of the two molecules, both trifluoromethyl groups of the 3,5-bis(trifluoromethyl)phenyl substituent are disordered over two positions. In [3,5-bis(trifluoromethyl)phenyl]bis[2,6-bis(trifluoromethyl)phenyl]borane, C24H9BF18, (II), only one of the twometa-trifluoromethyl groups is disordered. In [2,6-bis(trifluoromethyl)phenyl]bis[3,5-bis(trifluoromethyl)phenyl]borane, C24H9BF18, (III), bothmeta-trifluoromethyl groups of only one 3,5-bis(trifluoromethyl)phenyl ring are disordered. [3,5-Bis(trifluoromethyl)phenyl]dimesitylborane, C26H25BF6, (IV), carries only onemeta-trifluoromethyl-substituted phenyl ring, with one of the two trifluoromethyl groups disordered over two positions. In addition to compounds (I)–(IV), the structure of bis[2,6-bis(trifluoromethyl)phenyl]fluoroborane, C16H6BF13, (V), is presented. None of theortho-trifluoromethyl groups is disordered in any of the five compounds. In all the structures, the boron centre is in a trigonal planar coordination. Nevertheless, the bond angles around this atom vary according to the bulkiness and mutual repulsion of the substituents of the phenyl rings. Also, theortho-trifluoromethyl-substituted phenyl rings usually show longer B—C bonds and tend to be tilted out of the BC3plane by a higher degree than the phenyl rings carryingorthoH atoms. A comparison with related structures corroborates the conclusions regarding the geometric parameters of the boron centre drawn from the five structures in this paper. On the other hand, CF3groups inmetapositions do not seem to have a marked effect on the geometry involving the boron centre. Furthermore, it has been observed for the structures reported here and those reported previously that for CF3groups inorthopositions of the aromatic ring, disorder of the F atoms is less probable than for CF3groups inmetaorparapositions of the ring.