Cationic titanium monofluorides TiFn+ (n = 1-3)have been examined by mass spectrometric and theoretical methods, with particular attention being given to the question of the thermochemical stability of the multiply charged species. Diatomic TiFn+ cations can be generated by dissociative electron ionization of titanium(IV) fluoride. In addition, long-lived TiF2+ and TiF3+ are accessible by charge-stripping mass spectrometry of mass-selected mono-and dications, respectively. This method also allows the measurement of the corresponding vertical ionization energy (IEv), which were determined as IEv(TiF+) = 15.2 +/- 0.3 eV and IEv(TiF2+) = 28 +/- 3 eV. These values are in agreement with those obtained from high-level ab initio calculations. Thus, TiF2+ is a thermochemically stable diatomic dication, while TiF3+ trication is metastable with respect to the Ti2+ + F+ asymptote. No evidence for Coulomb explosion was observed, suggesting a very long lifetime for this triply charged diatomic. Theory further predicts the existence of ZrF3+ in the gas phase, which, however, is also metastable with respect to charge separation into Zr2+ + F+.