The synthesis and characterization of a novel class of linear poly(alkyl aryl) ethers containing 1,2,3-triazolyl and perfluorocyclobutyl units have been described. These polymers were readily prepared from the Huisgen’s 1,3-dipolar cycloaddition of poly(ethylene glycol) diazides and 1,2-bis(4-ethynylphenoxy)perfluorocyclobutane that is defined as ‘click chemistry’ recently. These polymers exhibited relatively small polydispersity, good thermal stability and solubility in common organic solvents.