Two novel acidic cation-exchange resins, namely, NKC-9 and D072, were first developed to catalyze the esterification of acetic acid with methanol. Kinetics of methyl acetate synthesis are determined by the experiments in a batch reactor at temperatures from 45 to 60 degrees C under atmospheric pressure, with molar ratio of reactants (theta(Bo) = n(methanol):n(acetic acid)) from 0.8 to 1.3. The kinetic data are correlated with the Q-H, E-R, and LHHW and pseudohomogeneous (P-H) models. Then, the reactive distillation process for methyl acetate synthesis is simulated by the Aspen Plus process simulator. Lifetime evaluation of NKC-9 was carried out to study the conversion rate of acetic acid and selectivity of methyl acetate during the long-period running in the fixed-bed reactor. Finally, a series of characterizations such as Fourier transform infrared spectroscopy, X-ray diffraction, and polarizing microscopy were performed to investigate the structure and properties of NKC-9.