The adsorption of Na+ on gamma-alumina surfaces at four coverages of Na2CO3[5, 10, 15 and 20% w/w)] was characterized by solid-state 23Na and 27Al nuclear magnetic resonance (NMR) spectroscopy. The experimental results suggest that two distinct adsorbed species are present on the alumina surface: surface species and surface salts. At the lower coverages of Na2CO3 (5 and 10%), the surface species is predominant, in which the Na+ cations are associated with the oxygen atoms of gamma-alumina. Increasing the loading level to 15% results in the appearance of a second adsorbed species that is attributed to the surface salt, Na2CO3, deposited on the solid surface. Further adsorption of Na2CO3 leads to an increase in the amount of surface salt while the amount of surface species remains unchanged. 1H-27Al Cross-polarization magic angle spinning (CP-MAS) experiments give the evidence that some Na+ cations in the form of surface species are coordinated with the Brönsted acid sites of gamma-alumina. This may be the main driving force that improves appreciably the catalytic efficiency of an Na2CO3-Al2O3 catalyst.