Hydrophobic　metal-organic　frameworks　(MOFs)　not　only　have　high　water　stability,　but　also　exhibit　high　adsorption　capacity　towards　organic　molecules,　in　particular　hydrocarbons.　Herein　we　report　a　rare　metal　fluoride　organic　framework　MFOF-1　with　high　hydrophobicity,　which　is　constructed　from　unprecedented　fluoride-　and　sulfate-bridged　cubane-type　tetranuclear　cobalt　clusters.　MFOF-1　consists　of　three　types　of　polyhedral　cages　with　face-sharing　configurations,　and　possesses　a　novel　(3,9)-connected　3D+3D→3D　self-interpenetrating　array　or　the　rare　pyr　topology.　MFOF-1　shows　high　thermal　stability　and　high　stability　in　water　and　even　acid/base　aqueous　solutions,　and　exhibits　rather　high　H2and　CO2storage　capacities　at　ambient　pressure.　Remarkably,　MFOF-1　shows　little　adsorption　of　water　but　considerably　high　uptakes　of　methanol,　n-hexane,　cyclohexane,　and　benzene,　and　exhibits　a　certain　degree　of　adsorption　selectivity　of　benzene　over　cyclohexane.　©　2016　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim