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We report that linker ligand substitution involving just one atom induces a shape‐memory effect in a flexible coordination network. Specifically, whereas SIFSIX‐23‐Cu, [Cu(SiF6)(L)2]n, (L=1,4‐bis(1‐imidazolyl)benzene, SiF62−=SIFSIX) has been previously reported to exhibit reversible switching between closed and open phases, the activated phase of SIFSIX‐23‐CuN, [Cu(SiF6)(LN)2]n (LN=2,5‐bis(1‐imidazolyl)pyridine), transformed to a kinetically stable porous phase with strong affinity for CO2. As‐synthesized SIFSIX‐23‐CuN, α, transformed to less open, γ, and closed, β, phases during activation. β did not adsorb N2 (77 K), rather it reverted to α induced by CO2 at 195, 273 and 298 K. CO2 desorption resulted in α′, a shape‐memory phase which subsequently exhibited type‐I isotherms for N2 (77 K) and CO2 as well as strong performance for separation of CO2/N2 (15/85) at 298 K and 1 bar driven by strong binding (Qst=45–51 kJ/mol) and excellent CO2/N2 selectivity (up to 700). Interestingly, α′ reverted to β after re‐solvation/desolvation. Molecular simulations and density functional theory (DFT) calculations provide insight into the properties of SIFSIX‐23‐CuN. [ABSTRACT FROM AUTHOR]