The synthesis and characterization of an original class of linear poly(alkyl aryl) ethers containing 1,2,3-triazolyl and fluorinated moieties based on oligo(tetrafluoroethylene) telomer are presented. These polymers were prepared, from alpha,omega-dipropargyl ether bisphenol AF and 1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane, in 62% overall yields via the azide/alkyne "click" reaction and/or oxidative coupling of acetylenes (Hay reaction). The latter reactant was produced from the ethylene end-capping of oligo(tetrafluoroethylene) followed by a nucleophilic substitution with sodium azide. A simple tuning of the reaction conditions allowed us to direct the originally favored "click" reaction toward a competitive homocoupling of the terminal alkynes, thus leading to copolymers with drastically different structures, as evidenced by size exclusion chromatography, DSC, Raman, and UV-vis spectroscopy. Hence, original poly(alkyl aryl) ether copolymers with it high thermal stability (higher than 300 degrees C) that exhibit alternating statistic or block microstructures were obtained.