A hydrolytically stable MOF material, named KAUST-7’, was derived from a structural phase change of KAUST-7 upon exposure to conditions akin to protonic conduction (363 K / 95% Relative Humidity). KAUST 7’ exhibited a superprotonic conductivity as evidenced by the impedance spectroscopic measurement revealing an exceptional conductivity up to 2.0 x 10-2 S.cm-1 at 363 K and under 95% RH, a performance maintained over 7 days. Ab initio Molecular Dynamics simulations suggested that the water-mediated proton transport mechanism is governed by water assisted reorganization of the H-bond network involving the pending fluorine moieties in KAUST-7’ and the guest water molecules. The notable level of performances combined with a very good hydrolytic stability positions KAUST-7’ as a prospective proton-exchange membrane alternative to the commercial benchmark Nafion. Furthermore, the remarkable RH sensitivity of KAUST-7’ conductivity, substantially higher than previously reported MOFs, offers great opportunities for deployment as a humidity sensor.