para-Substitution reactions on C6F5 rings of Lewis acids have been exploited to achieve triply substituted derivatives. The reaction of B(C6F5)3 with P(SiMe3)3 ultimately affords the Lewis acid B(C6F4P(SiMe3)2)31. This species binds Lewis bases affording the adducts LB(C6F4P(SiMe3)2)3 (L = MeCN 2, OPEt33, PMe34, PBu35) and reacts with LiMe to give the salt [Li][MeB(C6F4P(SiMe3)2)3]·3THF 6. It also reacts with H2O to give (L)B(C6F4PH2)3 (L = H2O 7, MeCN 8). In an analogous fashion, [(C6F5)3PF][B(C6F5)4] was converted to [FP(C6F4P(SiMe3)2)3] [B(C6F5)4] 9 and subsequently to [(MeO)P(C6F4PH2)3][B(C6F5)4] 10.