In the presence of catalytic amounts of a secondary amine (e.g. morpholine), skipped diynones undergo hydration/cyclization in aqueous acetonitrile to form γ‐pyrones in moderate to excellent yields. The first step of the process involves a trans‐stereoselective conjugate‐addition of morpholine to the ynone. Gradually the intermediate E‐enaminone reacts with H2O yielding a hydration product via nucleophilic vinylic substitution. Then the amine adds to the second ynone moiety and the resulting enaminone is attacked intramolecularly by the enol hydroxyl to yield the γ‐pyrone, with elimination of morpholine (regeneration of the catalyst). Primary amines fail to promote the process, as the initially formed Z‐configurated enaminones are reluctant to react further under standard reaction conditions.