Membranes with outstanding performance that are applicable in harsh environments are needed to broaden the current range of organics dehydration applications using pervaporation. Here, well-intergrown UiO-66 metal-organic framework membranes fabricated on pre-structured yttria-stabilized zirconia hollow fibers is reported via controlled solvothermal synthesis. On the basis of adsorption-diffusion mechanism, the membranes provides a very high flux of up to ca. 6.0 kg m-2 h-1 and excellent separation factor (> 45000) for separating water from i-butanol (next-generation biofuel), furfural (promising biochemical) and tetrahydrofuran (typical organic). This performance, in terms of separation factor, is one to two orders of magnitude higher than that of commercially available polymeric and silica membranes with equivalent flux. It is comparable to the performance of commercial zeolite NaA membranes. Additionally, the membrane remains robust during a pervaporation stability test (~300 hours), including exposure to harsh environments (e.g., boiling benzene, boiling water and sulfuric acid) where some commercial membranes (e.g., zeolite NaA membranes) cannot survive.