A novel method for the detection of synthetically useful pentacarbonyl chromium and tungsten carbene complexes by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry is presented which utilizes the addition of CN- anions to the electrophilic carbene carbon. This method is nondestructive, provided the ionization proceeds under soft conditions. The scope and limitations of this method are examined by utilizing different types of carbene complexes. Depending on the α-CH acidity of the carbene complexes, [M − H]- anions can be observed either in competition with the CN- adducts or as the only ions, even in the presence of cyanide. Secondary aminocarbene complexes exclusively form [M − H]- anions by deprotonation of the NH moiety. The ions under study have been mass-selected and subjected to collision-induced decay (CID) experiments in order to examine their fragmentation reactions. CO loss is not the only observable process. Most prominently, 1,2-eliminations and a retro-aldol reaction within a sugar carbene complex compete with decarbonylation and thus have rather low activation barriers. Some reactions can be attributed to coordinatively unsaturated chromium atoms formed through preceding CO losses.