The fragmentation pathways and mechanisms for 27 ferrocene carbamate esters of saturated alkyl primary, secondary and tertiary alcohols were investigated using energy-resolved electrospray tandem mass spectrometry (ES-MS/MS). The mechanisms that control the formation and abundance of the three product ions common to all the derivatives, which appear at m/z 201, 227 and 245, were elucidated. Plotting the relative abundances of the three product ions versus a range of center-of-mass collision energies provided a graphical representation of the behavior of the fragmentation process that was directly comparable from compound to compound. As a result, it was possible to compare product ion spectra of the different derivatives to distinguish among different alcohol structural types. Straight-chain primary alcohols were easily distinguished from tertiary alcohols. Both of these structural types, including positional isomers, produced product ion spectra that were distinct from those of beta-branched primary alcohols, or acyclic secondary alcohols or cyclic secondary alcohols. The latter three alcohol types display similar product ion spectra and therefore cannot be distinguished from one another on the basis of these spectra alone.