Protocols for the synthesis of the bulky polyfluorinated triarylboranes 2,6-(C₆F₅)₂C₆F₃B(C₆F₅)₂ (1), 2,6-(C₆F₅)₂C₆F₃B[3,5-(CF₃)₂C₆H₃] (2), 2,4,6-(C₆F₅)₃C₆H₂B(C₆F₅)₂ (3), 2,4,6-(C₆F₅)₃C₆H₂B[3,5-(CF₃)₂C₆H₃] (4) were developed. All boranes are water tolerant and according to the Gutmann-Beckett method, 1–3 display Lewis acidities larger than that of the prominent B(C₆F₅)₃.