Di- and multiazole-substituted fluorocyclic products (2–13) were readily synthesized in good to high yields. These were synthesized by nucleophilic substitution reactions of perfluorocycloalkenes with azoles (i.e., imidazole, triazole) involving simple reaction procedures. Interestingly, these azoles were later found to be reactive not only with the vinylic, but also with the allylic fluorine atoms. This resulted in the substitution of up to six azoles on the fluorinated rings. Stoichiometry plays a key role in determining the degree of substitution. For comparison, the analogous reactions of N-substituted 1-(trimethylsilyl)-imidazole and 1-(trimethylsilyl)-1,2,4-triazole were also investigated. All of the new compounds were fully characterized by elemental, spectral (19F, 1H, 13C NMR), and thermal differential scanning calorimetry (DSC) analyses.