SBA-15 silica supported rhenium catalysts were synthesized using solution-based atomic layer deposition method, and their activity and stability were studied in the acid-catalyzed 2-butanol dehydration. We find that ReO x /SBA-15 exhibited an extremely high initial activity but a fast deactivation for 2-butanol dehydration at 90−105°C. Fast deactivation was likely due to the sintering, sublimation, and reduction of rhenia as confirmed by TEM, elemental analysis, and in situ UV−vis (DRS) measurements. To overcome these issues, ReO x /AlO x / SBA-15 catalysts with significantly improved stability were prepared by first modifying the surface identity of SBA-15 with alumina followed by dispersion of rhenia using atomic layer deposition. The AlO x phase stabilizes the dispersion of small and uniform rhenia clusters (<2 nm) as as confirmed by TEM, STEM, and UV−vis (DRS) characterizations. Additional 27 Al MAS NMR characterization revealed that modification of the SBA-15 surface with alumina introduces a strong interaction between rhenia and alumina, which consequently improves the stability of supported rhenia catalysts by suppressing the sintering, sublimation, and reduction of rhenia albeit at a moderately reduced initial catalytic dehydration activity.