The dehydrofluorination of 2H,3H-decafluoropentane (HFC-4310mee) using 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) selectively gave (Z)-2H-nonafluoropent-2-ene as a bench-stable volatile liquid. Nucleophilic substitution reactions of (Z)-2H-nonafluoropent-2-ene with allylic alcohols gave the corresponding polyfluorinated allylic vinyl ether derivatives. The Claisen rearrangement of the polyfluorinated allylic vinyl ethers smoothly proceeded under ambient conditions to give polyfluorinated homoallylic ketones quantitatively. These results indicate the potential of 2H,3H-decafluoropentane as an inexpensive and easy-to-handle chemical feedstock for the syntheses of densely functionalized polyfluorinated organic compounds.