The synthesis of methyl salicylate (MS) from salicylic acid (SA) and dimethyl carbonate (DMC) was performed over a series of mesoporous aluminosilicates. The results showed that mesoporous aluminosilicate was an effective esterification catalyst for the reaction. It was also found that both SA conversion and MS selectivity were closely linked with the intermediate strong acidity and Lewis acidity of catalysts. As a result, the synergistic mechanism was proposed for the esterification of SA with DMC over a mesoporous aluminosilicate.