Abstract: A convenient method for the synthesis of network polymeric crown ethers containing side group on network unit starting from non-crown ether monomers has been reported.Thus,six new network polymeric crown ethers have been synthesized by ring-opening copolymerization of ethylene glycol bisglycidyl ether and various monoglycidyl ethers in the presence of ( i-Bu)₃Al/H₃PO₄/H₂O/PhN(CH₃ )₂ as catalyst,respectively.The obtained polymers possess good complexing capacities for sodium and potassium ion and most of them show effective PTCactivity in the nucleophilic substitution of BuBr by PhOKin triphase system.