Relative intensities of singly-charged mono-bromide silver clusters Ag
x
Br+ formed from sputtering of a pressed pellet of silver bromide were measured by mass spectrometry. The obtained results suggest that the Ag
x
Br+ clusters have a structural formula of the form Agx–1+(AgBr). The relative stability of Agx–1+(AgBr) was determined by the intrinsic stability of the remaining metallic portion of the cluster (Agx–1+) as predicted by the spherical jellium model (SJM). Unimolecular and high-energy collision-induced dissociation (CID) spectra of Ag
x
Br+ (x = 2, 4, 6, 8, 10) clusters were also measured. In all of the spectra, the most intense fragment peaks were assigned to the Agx–1+ ions accompanying the loss of AgBr. The difference in the relative intensities of the Agx–1+ peaks between unimolecular dissociation and CID spectra led us to conclude that the weakest bond in the excited cluster Ag
x
Br+* is the Agx–1+–AgBr bond and the structure of Ag
x
Br+ is a metallic Agx–1+ ion cluster adduct with AgBr. The primary fragments observed in the CID spectra were also explained by the stabilities of the generated ion products and neutral fragments, both having even delocalized valence electrons. The present results were consistently explained by SJM. The dissociation behavior of Ag2Br+ can be explained on the basis of the calculated thermochemical data.