Abstract: The synthetic method and properties of a series of new network polymeric crown ethers were reported in this paper. Eight network polymeric crown ethers were prepared by the net-polymerization of bisglycidyl ether, ethylene glycol bisglycidyl ether, diethy-lene glycol bisglycidyl ether triethylene glycol bisglycidyl ether and tetraethylene glycol bisglycidyle ther in the presence of BF₃·OEt₂ or (i-Bu)₃Al as catalyst. The studied network polymeric crown ethers have good cation-complexing ability and effective catalytic activity in the nucleophilic substitution of PhOK with n-BuBr.