Ethyl acrylate (EA) is synthesized by ethyl acetate (EtOAc) with formaldehyde (FA) through aldolcondensation withfixed-bed reactor, and a series of Ce–P–Cs/g-Al2O3 catalyst was developed. Thecatalysts were characterized with XRD, XPS, SEM-EDS, NH3- and CO2-TPD, BET, and pyridine FTIR. Theinfluence of acidity and basicity on activity was discussed. Catalytic performances were further improvedby the addition of small amounts of Ce. Key reaction parameters, such as amount of metal loading, spacevelocity and reaction temperature, were also optimized. The optimum condition demonstrated amaximum EA yield of 31.38% and 60.03% selectivity toward EA.