In this paper, the supported phase transfer catalytic polyester fabric was prepared by dip-rolling with acrylate copolymer as modifier and polyester fabric as carrier. The catalytic performance and reaction mechanism for Williamson ether synthesis reaction with the catalytic fabric were analyzed. The effects of cross-linking of copolymers, length of hydrophobic alkyl chain, cationic structure, cationic content and loading amount of the modifier on the catalytic activity for the modified fabric were investigated. The results show that phosphoric acid and glycerin can improve the crosslinking degree of copolymer molecules, thus improving the catalytic stability of the catalytic fabric; the excellent catalytic activity of the modified fabric is observed when the length of hydrophobic chain ester is octadecyl ester, the cationic monomer is methylacrylamide propyldimethylbutylammonium bromide, the molar amount of the cationic monomer is 13.33% and the loading amount is 20%. The oil phase was adsorbed on the surface of the catalytic fabric, and the ion-exchange and bonding reactions were initiated. In Williamson ethers synthesis reaction with different phenols, the conversion rate can reach more than 92%. The catalytic activity has no obvious change after reused 10 times.