Charge exchange of neutral C3F6 by a variety of atomic and molecular ions in the 1 to 25 eV range of collision energies is used to characterize the energies associated with formation of [C3F6]+˙. The internal energy of the nascent [C3F6]+˙ ion, assessed by observing the degree to which it fragments, increases with the recombination energy of the charge‐exchange reagent. The existence of excited states of the reagent ions is identified from the fragmentation behaviour of [C3F6]+˙ in the cases of [CS2]+˙, NO+, O2+˙, [NH3]+˙ and possibly [CH4]+˙. In addition, the data confirm that the [C3F6]+˙ parent ion fragments from both the ground state and a long‐lived isolated electronic state. The latter is populated by near‐resonant charge transfer. Translational excitation contributes relatively little to internal excitation of the charge‐exchanged product ion and even less in the case of the isolated state.