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Long‐chain ferulic acid esters, such as eicosyl ferulate (1), show a complex and analytically valuable fragmentation behavior under negative‐ion electrospay collision‐induced dissociation ((‐)‐ESI‐CID) mass spectrometry, as studied by use of a high‐resolution (Orbitrap) mass spectrometer. In a strong contrast to the very simple fragmentation of the [M + H]+ ion, which is discussed briefly, the deprotonated molecule, [M ‐ H]‐, exhibits a rich secondary fragmentation chemistry. It first loses a methyl radical (MS2) and the ortho‐quinoid [M ‐ H ‐ Me]‐• radical anion thus formed then dissociates by loss of an extended series of neutral radicals, CnH2n+1• (n = 0‐16) from the long alkyl chain, in competition with the expulsion of CO and CO2 (MS3). The further fragmentation (MS4) of the [M ‐ H ‐ Me ‐ C3H7]‐ ion, discussed as an example, and the highly specific losses of alkyl radicals from the [M ‐ H ‐ Me ‐ CO]‐• and [M ‐ H ‐ Me ‐ CO2]‐• ions provide some mechanistic and structural insights.