The obtained results reveal simple synthetic approach for bidentate boron Lewis acids with the -OB(C6F5)2 acid group and aliphatic or aromatic linkers. Computational results showed comparable FIA for the -OB(C6F5)2 site in boron bidentate Lewis acids relative to initial B(C6F5)3. The relative Lewis acid strength of R[OB(C6F5)2]2 (R=C2H4, p-C6H4, m-C6H4) was characterized by Gutman-Beckett tests. The elimination of pentafluorobenzene by the reaction of R-OH with B(C6F5)3 can be used for the synthesis of R-OB(C6F5)2 derivatives and polydentate strong Lewis acids.