The crosslinked polymeric microspheres (GMA/MMA) of glycyl methacrylate (GMA) and methyl methacrylate (MMA) were prepared by suspension polymerization. Polyethylene glycol (PEG) was grafted on GMA/MMA microsphers via the ring-opening reaction of the epoxy groups on the surfaces of GMA/MMA microspheres, forming a polymer-supported triphase catalyst, PEG-GMA/MMA. The Phase-transfer catalytic activity of PEG-GMA/MMA microspheres was evaluated using the esterification reaction of n-chlorobutane in organic phase and benzoic acid in water phase as a model system. The effects of various factors on the phase transfer catalysis reaction of liquid-solid-liquid were investigated. The experimental results show that the PEG-GAM/MMA microspheres are an effective and stable triphase catalyst for the esterification reaction carried out between oil phase and water phase. The polarity of the organic solvent, the ratio of oil phase volume to water phase volume and the density of the grafted PEG on PEG-GMA/MMA microspheres affect the reaction I-ate greatly. For this investigated system, the solvent with high polarity is appropriate, an adequate volume ratio of oil phase to water phase is 2:1, and the optimal PEG density on the polymeric microspheres is 15 g/100 g. Triphase catalysts offer many advantages associated with heterogeneous catalysts such as easy separation from the reaction mixture and reusability. The activity of PEG-GMA/MMA microspheres is not nearly decreased after reusing of 10 recycles. (C) 2009 American Institute of Chemical Engineers AIChE J, 56: 729-736, 2010