A novel adsorbent was prepared by NH4HCO3-modifying nanoalumina dioxide and was employed for the separation/preconcentration of Re-VII ions from aqueous solution. It was found that Re-VII ions could be adsorbed quantitatively (above 94%) on modified nano-Al2O3 in the pH range of 2.0-3.0, while only 8.3% of Re-VII ions were adsorbed on unmodified nano-Al2O3. Effects of the pH, concentration of elution solution, and interfering ions on the recovery of Re-VII were systematically investigated. Adsorption kinetics for Re-VII was found to be very fast, and equilibrium was reached within 5 min following the pseudo-second-order model with observed rate constants (k(2)) of 14.44 g.mg(-1).min(-1) at 298 K. The overall rate process appeared to be influenced by both external mass transfer and intrapartide diffusion. The sorption data could be well interpreted by the Langmuir model with a maximum adsorption capacity of 1.94 mg.g(-1) of Re-VII on modified nano-Al2O3. Moreover, the thermodynamic parameters showed the spontaneous and endothermic nature of the adsorption process. Finally, modified nano-Al2O3 as the sorbent was successfully applied to the separation of Re-VII from the ore samples with satisfactory results.