The results of studying the emission and fragmentation of niobium-carbon clusters Nb m C n + synthesized upon sputtering a niobium carbide surface with Xe+ ions are presented. The fragmentation channels of Nb m C n + clusters are studied. We present the values of the dissociation energy of some Nb m C n + clusters (m = 1–7, n = 2–8) calculated within the context of the “evaporation ensemble” model and theory of unimolecular reactions based on performed measurements of the kinetic-energy spectra of fragment ions. The obtained results are compared with published data.