The bare amorphous Al 2 O 3 -AlPO 4 and Cs/Al 2 O 3 -AlPO 4 catalysts were developed for the aldol condensation of methyl acetate with formaldehyde to methyl acrylate. The structure and property of catalyst were characterized by XRD, XPS, BET, Pyridine-IR, FT-IR, 27 Al-MASNMR, NH 3 -/CO 2 -TPD and SEM. The correlation between structural features and acid-base properties was established, and the loading effect of the cesium species was investigated. Due to cooperative catalytic effects between the penta-coordinated Al and Al 2 O 3 , the weak-Ⅱ acid and medium acid site densities and the product selectivity were improved. While the basic site densities of these catalysts were almost in proportion to the conversion of methyl acetate. The loaded Cs could form new basic sites and change the distribution of acid sites which further enhance the catalytic performance. As a result, the 10Cs/8AlP was proved to be an optimal catalyst with the yield and selectivity of 21.2% and 85% for methyl acrylate respectively. During the reaction, a deactivation behavior was observed on 10Cs/8AlP catalyst due to the carbon deposition, however, it could be regenerated by thermal treatment in the air atmosphere at 400 °C.