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Water stability is one of the most important factors restricting the practical application of metal organic frameworks (MOFs). In this work, we fabricate a highly defective HKUST-1 framework with a mixed valence of CuI/CuII by mechanical ball milling method. This defective HKUST-1 is embellished by functionalized ionic liquids as hydrophobic armor, making the hybrid HIL1@HKUST-1 exhibits outstanding water stability, remarkable SO2 adsorption (up to 5.71 mmol g−1), and record-breaking selectivity (1070 for SO2/CO2 and 31,515 for SO2/N2) at 25 °C and 0.1 bar, even in wet conditions.