Aromatic six-membered imides suffer the introduction of bulky substituents at the imide-positions due to formation of isoimides and low reactivity, preventing from the investigation of the intrinsic molecular properties. Here, we found a highly efficient alcohol-promoted re-arrangement from isonaphthalimide to naphthalimide in acid or basic nonaqueous conditions, which can be regarded as model com-pounds for aromatic six-membered imides. We proposed two-step nucleophilic substitutions in the isomerization mechanistic pathways that were verified by the separation of a key intermediate. Furthermore, in-situ 1H NMR exhibited the first-order kinetics for the isoimide loss process. Finally, the alcohol-promoted isoimide-imide rearrangement was extended to a palladium-catalyzed one-pot domino car-bonylation reaction toward sterically crowded aromatic six-membered imides.