Shielding metal sites of Cu‐ <scp>BTC</scp> to achieve reversed benzene/vinyl acetate selectivity for trace benzene removal

Abstract Removal of trace benzene (Bz) is critical for ensuring extensive applications of vinyl acetate (VA), however, is challenging due to the specific properties of this binary mixture. This study presents an “exposure + shielding” modification strategy for Cu‐BTC, involving acetic acid fragmentation and glycine grafting, to enhance the contribution of ligands in Bz adsorption. Comprehensive characterizations confirm the structural integrity and tailored porosity of modified adsorbents. Compared to pristine Cu‐BTC, Gly(1.00)@Ac/Cu‐BTC demonstrates a 69.7% increase in static uptake and nearly twofold improvement in breakthrough capacity. Gly(1.00)@Ac/Cu‐BTC also exhibits superior thermal stability (up to 583 K) and chemical stability in VA, with no decomposition after 30 days. DFT calculations reveal a reversed Bz/VA selectivity, driven by enhanced π‐complexation and effective shielding of Cu sites. This work represents the first example to achieve the practical Bz/VA separation, and highlights the potential of synergistic modifications in designing efficient, stable MOFs for industrial separations.