1,n-Dual Π systems including 1,4-diene derivatives have been widely used as the elegant radical receptors to promote cascade radical additions to give the highly functionalized polycyclic scaffolds. However, the tedious and complicated preparation of the former deters broad utilization and compromises the practical value. Herein, a straightforward preparation of 1,4-diene derivatives was developed from the easily accessible alkynes and γ,δ-unsaturated carboxylic acids via electrochemical oxidation cyclization and Hofmann elimination. This transformation features with good to excellent yields, functional group compatibility, and selectivity without any Zaitsev elimination product detected.