Two types of catalysts, V2O5-P2O5/SiO2 and Cs-Sb2O5/SiO2, were separately prepared with SiO2 as carrier. Their catalytic properties were investigated in the process of synthesizing methyl acrylate through aldol condensation with methylal and methyl acetate, and the influence of the catalyst’s filling up technique on the reaction was studied. Reactions were performed in a fixed-bed reactor. The research results indicate that aldol condensation reaction is effectively promoted when the two catalysts were filled up in appropriate subsections of the reaction tube. Specifically, when V-Si-P Oxide was filled up at the 4th subsection and Cs-Sb2O5/SiO2 catalyst at the 6th subsection with the temperature of the reactor at 400 °C and the mol ratio of methyl acetate and methylal at 1.6:1 and the space velocity at 3.2 h-1, then the conversion rate of methylal was 50.9%, the selectivity of methyl acrylate was 90.63%, and the ester yield of methyl acrylate was 46.15%.