The reaction kinetics of transesterification of methyl acetate with isobutanol catalyzed by ionic liquid 1-sulfobutyl-3-methylimidazolium hydrogensulfate was measured. The reaction kinetic data were correlated by the ideal homogeneous model and nonideal homogeneous model, and the corresponding kinetic parameters were obtained. A reactive and extractive distillation (RED) process was proposed to conduct the transesterification, and the process was simulated based on the analysis of vaporliquid equilibrium and reactive residue curve maps. High purities of products and high conversions of reactants can be achieved by the RED process. Effects of operating and structural parameters of the RED column and entrainer recovery column were investigated. Moreover, a lab-scale RED experiment was conducted to verify the reliability of the simulation process, and the simulation results agreed well with the experiment.