Mono-, bis-, and tris(trifluoromethane-sulfonate ester)s ((triflate ester)s) were prepared by the reaction of benzyl alcohol (1), 1,4-bis(hydroxymethyl)-benzene (2) and 1,3,5-tris(hydroxymethyl)benzene (3) with trifluoromethanesulfonic anhydride in the presence of 2,6-di-tert-butylpyridine. These benzylic triflate esters were applied in-situ for the living polymerization of tetrahydrofuran (THF). The subsequent end-capping reaction with a suitable nucleophile proceeded quantitatively to produce mono. bi- and, in particular, novel trifunctional telechelic poly(THF)s, respectively.