1H/23Na double resonance NMR techniques were employed to study the modification of surface hydroxyls on Y-Al2O3 by sodium ions. 1H-23Na cross polarization (CP) experiment can resolve three kinds of sodium cations that are closely associated with surface hydroxyl groups, while the signal of deposited salt-Na2CO3, which is not connected to surface hydroxyl groups, is completely suppressed. 1H{23Na} spin echo double resonance experiments reveal the surface modification in more detail. At low Na+ coverage (5%, 10%), the acidic hydroxyl groups are preferentially coordinated with sodium ions, while both the acidic and the basic hydroxyl groups are accessible for sodium ions at highcoordination that causes proton of the OH groups to be easily dissolved, which is evidenced by the fact that with calcination temperature of the catalysts increasing, the acidic hydroxyl groups are preferentially removed and only the basic hydroxyl groups remain when the calcination temperature is raised to 600℃. 1H / 23Na double resonance NMR techniques were employed to study the modification of surface hydroxyls on Y-Al2O3 by sodium ions. 1H-23Na cross polarization (CP) experiment can resolve three kinds of sodium cations that are closely associated with surface hydroxyl groups, while 1H (23Na} spin echo double resonance experiments reveal the surface modification in more detail. At low Na + coverage (5%, 10%), which is not connected to the surface hydroxyl groups the acidic hydroxyl groups are preferentially coordinated with sodium ions, while both the acidic and the basic hydroxyl groups are accessible for sodium ions at highcoordination that causes proton of the OH groups to be readily dissolved, which is evidenced by the fact that with calcination temperature of the catalysts increasing, the acidic hydroxyl groups are preferentially removed and only the basic hydroxyl groups remain when the calcination temperature is raised to 600 ° C.