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Biofuels are considered sustainable and renewable alternatives to conventional fossil fuels. Biobutanol has recently emerged as an attractive option compared to bioethanol and biodiesel, but a significant challenge in its production lies in the separation stage. The current industrial process for the production of biobutanol includes the ABE (acetone–butanol–ethanol) fermentation process from biomass; the resulting fermentation broth has a butanol concentration of no more than 2 wt% (the rest is essentially water). Therefore, the development of a cost-effective process for separation of butanol from dilute aqueous solutions is highly desirable. The use of porous materials for the adsorptive separation of ABE mixtures is considered a highly promising route, as these materials can potentially have high affinities for alcohols and low affinities for water. To date, zeolites have been tested toward this separation, but their hydrophilic nature makes them highly incompetent for this application. The use of metal–organic frameworks (MOFs) is an apparent solution; however, their low hydrolytic stabilities hinder their implementation in this application. So far, a few nanoporous zeolitic imidazolate frameworks (ZIFs) have shown excellent potential for butanol separation due to their good hydrolytic and thermal stabilities. Herein, we present a novel, porous, and hydrophobic MOF based on copper ions and carborane–carboxylate ligands, mCB-MOF-1, for butanol recovery. mCB-MOF-1 exhibits excellent stability when immersed in organic solvents, water at 90 °C for at least two months, and acidic and basic aqueous solutions. We found that, like ZIF-8, mCB-MOF-1 is non-porous to water (type II isotherm), but it has higher affinity for ethanol, butanol, and acetone compared to ZIF-8, as suggested by the shape of the vapor isotherms at the crucial low-pressure region. This is reflected in the separation of a realistic ABE mixture in which mCB-MOF-1 recovers butanol more efficiently compared to ZIF-8 at 333 K., L.G., P.G.F., F.T., C.V., and J.G.P. thank MINECO grant CTQ2016-75150-R and the Generalitat de Catalunya (2017/SGR/1720) for financial support. H.H. acknowledges financial support from the National Natural Science Foundation of China (No. 21978212). ICMAB receives support from the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2015-0496. L.G. is enrolled in the UAB Ph.D. program. L.G. acknowledges the China Scholarship Council (CSC) for his Ph.D. grant (201609110106). K.C.S. thanks the Department of Chemistry at Oregon State University for support through start-up funding. J.A.R.N. thanks MINECO and the UE Feder Program (project CTQ2017-84692-R). Some of the experiments were performed at the XALOC and NCD-SWEET beamlines of the ALBA synchrotron with the support of ALBA staff. We thank Bardiya Valizadeh for his assistance with measuring the contact angles