Different synthetic methods for the preparation of polyfunctional fluorinated oligomers were explored and the results compared. Fluoropolyether macromonomers bearing epoxy, allyl, and polyhydroxy end groups were synthesized and spectroscopically characterized. For obtaining a polyol (namely tetraol) functionality, a highly selective route was the reaction of the fluoropolyether macrodiol ZDOL with allylic halides and subsequent oxidation reaction at the C=C double bond by means of peroxyacids. This approach made it possible to obtain a segmented structure RH-RF-RH in which the molecular body RF consisted of a perfluoropolyether block endcapped by two hydrogenated segments RH, where RH = - CH2OCH2CH(OH)CH2OH. Unlike other more conventional syntheses, which always produce byproducts and higher molecular weight species such as RH-(RF-RH)(n)-RF-RH or RH-RF-(RH)(n)-, the described method offers high yields and selectivity. The fluoropolyether polyfunctional derivatives offer the possibility to prepare a variety of highly crosslinked fluorinated materials and, owing to their well defined regularly segmented structures, they also constitute interesting models for the understanding of basic structure-property relations of fluoro-oligomers and their copolymers.