Structural changes of aromatic imides upon one-electron reduction are investigated by time-resolved resonance Raman spectroscopy during pulse radiolysis. Significant downshifts are observed for both the aromatic ring stretching and carbonyl stretching modes, which are related to a reduction of the bond order and increase of the charge density on these moieties. For three aromatic imides, i.e., 1,8-naphthalene imide (1,8-NI), 2,3-naphthalene imide (2,3-NI), and naphthalene diimide (NDI), the extent of structural changes is found to follow the order: 2,3-NI > 1,8-NI > NDI, reflecting the influence of charge distribution on molecular structure. To further investigate this phenomenon, a series of homologous NDI derivatives with a substituted phenyl group at the imide position are studied. The Raman peaks between 1550 and 1600 cm-1, which are assigned to aromatic stretching vibrations of the NDI moieties, are found to be sensitive to the charge distribution: stronger electron-withdrawing substituents result in these peaks shifting to slightly higher wavenumbers. As supported by a spin density analysis, despite the fact that the added charge is mostly localized on the NDI moiety, in the presence of an electron-withdrawing group, the subtle charge is likely to delocalize on the phenyl fragment, alleviating the effect of one-electron reduction on the molecular structure.