We present a combined theoretical and experimental study of cationic sodium fluoride clusters stability. The dissociation channels of Na+(NaF)(n), n = 3-11, have been measured from unimolecular decay experiments. Binding and dissociation energies have been calculated using a simple potential. The discussion of the observed dissociation channels in the light of their relative binding energy reveals that entropic and kinetic effects play an important role in the fragmentation process. (c) 2005 Elsevier B.V. All rights reserved.