Using tunable vacuum-UV radiation from a synchrotron, the threshold photoelectron and threshold photoelectron photoion coincidence (TPEPICO) spectra of cyclic-C₄F₈ in the range 11–25 eV have been recorded. The parent ion is observed very weakly at threshold, 11.60 eV, and is most likely to have cyclic geometry. Ion yield curves and branching ratios have been determined for five fragments. Above threshold, the first ion observed is C₃F⁺₅, at slightly higher energy C₂F⁺₄, then successively CF⁺, CF⁺₂ and CF⁺₃ are formed. The dominant ions are C₃F⁺₅ and C₂F⁺₄, with the data suggesting the presence of a barrier in the exit channel to production of C₃F⁺₅ whilst no barrier to production of C₂F⁺₄. In complementary experiments, the product branching ratios and rate coefficients have been measured in a selected ion flow tube (SIFT) at 298 K for the bimolecular reactions of cyclic-C₄F₈ with a large number of atomic and small molecular cations. Below the energy where charge transfer becomes energetically allowed, only one of the ions, CF⁺₂, reacts. Above this energy, all but one of the remaining ions react. Experimental rate coefficients are consistently greater than the collisional values calculated from modified average dipole orientation theory. The inclusion of an additional ion–quadrupole interaction has allowed better agreement to be achieved. With the exception of N⁺, a comparison of the fragment ion branching ratios from the TPEPICO and SIFT data suggest that long-range charge transfer is the dominate mechanism for reactions of ions with recombination energy between 12.9 and 15.8 eV. For all other ions, either short-range charge transfer or a chemical reaction, involving cleavage and making of new bond(s), is the dominant mechanism.