Aminated natural polysaccharide materials with unique positive potential hold great applications in superabsorbent, isolation, purification etc. However, their existing preparation methods are also limited by the shortcomings of low grafting number of amino groups, complex preparation processes, high energy consumption. Here we report a one-pot method combining Maillard reaction (Increased amine grafting sites), epoxy-amino addition reaction and condensation crosslinking reaction (Increased conversion rate) for rapid and low-cost preparation of amine-modified crosslinked glucose (AMG) with large grafting amount (N atom.%=18.0%). AMG exhibits unique hydrophilic and tert-butanol-repellent effects, which can be used to break the azeotropic equilibrium of water-tert-butanol and improve the concentration of TBA by 5% through a simple distillation process. Comparative experiments and molecular dynamics simulations have confirmed that this separation performance comes from the different binding forces between AMG and small liquid molecules. In addition, AMG has demonstrated a large and selective adsorption removal capacity for anionic dyes.