A domino reaction comprising four consecutive steps based on the strategy of isomerization of allylic alcohols was developed. This base‐catalyzed protocol provided an approach for constructing polysubstituted quinolines without additional additives. A wide range of di‐ or trisubstituted γ‐aminoaryl allylic alcohols bearing alkyl or (hetero)aryl substituents were transformed to the structurally diverse quinolines. The utility of this transformation was demonstrated by the application in the concise synthesis of several polysubstituted quinoline derivatives, including natural products and pharmacological agents. Preliminary mechanistic experiments suggested that the isomerization of γ‐aminoaryl allylic alcohol underwent an intramolecular 1,3‐hydrogen shift and the aromatization of the dihydroquinoline intermediate went through two possible pathways simultaneously exist, acceptorless dehydrogenation and transfer hydrogenation process.