A novel and convenient route for the synthesis of phenylethenyl methyl carbonate by the methoxycarbonylation of phenylacetaldehyde with dimethyl carbonate was developed in the presence of solid base catalysts. The results showed that solid bases with moderate strength such as MgO favored the formation of phenylethenyl methyl carbonate, and the yield of phenylethenyl methyl carbonate could be linearly correlated with the amount of moderate basic sites. The function of basic catalysts was mainly ascribed to the activation of phenylacetaldehyde via the abstraction of -H by the base sites.