Catalytic distillation (CD) technology in hydrolyzing methyl acetate (MeOAc) in polyvinyl alcohol (PVA) production process was studied in this paper. Three operational variables, R-m-mole ratio of feed water to MeOAc, R-f-volume ratio of reflux to feed MeOAc and S-V-the ratio of the feed volume flow rate of MeOAc to the volume of catalyst bed, are defined and investigated in detail. Two parameters, R-con, the conversion of MeOAc, and R-A/W, the mass ratio of acetic acid to water in the hydrolysis mixture are also defined. They are used as indices for investigating the performance of the catalytic distillation. As a strong industrial backgrounded project, there is a premise that must be satisfied, that is the R-A/W cannot be less than 1.3. According to the experimental results, a set of operational parameters is recommended. The R-m ranges from 2 to 3, the R-f ranges from 3.0 to 5.5 and the S-V from 0.25 to 0.55. With the satisfaction of the R-A/W, the conversion of MeOAc by CD technology is as high as 56%, which is more than two times that of the fixed bed reactor (FBR) technology. If the R-A/W is not taken into account, complete conversion of MeOAc can gy be achieved easily with a high R-m.