A series of modified ZSM-5 catalysts were prepared for cross-aldol condensation of methyl acetate with formaldehyde- the simplest aldehyde without cc-H for the production of methyl acrylate (MA). The active components, such as P and Cs, were selected to modify ZSM-5 and the effect of active component load on the catalyst acid-base properties was associated with the yield of MA. The catalysts were characterized with X-ray diffraction, FT-IR, SEM, TEM, and NH3-TPD and changes of the catalyst structure and acid-base properties were explored. The thermodynamics calculation for the complex reaction was given to indicate the direction and the depth of the reaction. The formation of C-C bonds, key transition states and energy barrier were simulated to investigate the formation of ester enol form and the mechanism of aldol reaction process via quantum chemistry theory. Two forms of formaldehyde, namely, trioxymethylene and formalin, were applied to evaluate the catalysts in a fixed-bed micro-type reactor at the various reaction temperatures. The catalyst life and regeneration performance were investigated. (C) 2017 Elsevier Inc. All rights reserved.