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CO esterification to dimethyl oxalate (DMO) has important industrial application value. However, the influence of support on catalytic performance has not been investigated sufficiently. In this work, MgAl-LDO supports (MgAl-LDO-400 and MgAl-LDO-600) were prepared at different calcination temperatures. The corresponding Pd-based catalysts was synthesized by impregnation method. The Pd/MgAl-LDO-400 catalyst exhibited higher CO conversion (39%) compared with the Pd/MgAl-LDO-600 (16%). It was found that Pd/MgAl-LDO-400 catalyst contains more Lewis basic sites, which is responsible for its higher activity. This work provides a general understanding of the support effect on catalytic performance induced by the Lewis basic sites.