The diversity‐oriented organic synthesis of novel coumarin annulated tricyclic dioxocine, dioxacindione scaffolds with Z‐selectivity and the symmetrical pentacyclic coumarin macrocyclic derivatives is demonstrated from substituted hydroxyl coumarins via ring‐closing metathesis in the presence of Grubbs’ second‐generation catalyst as the facile and efficient route with excellent yields. This synthetic strategy provides a route for the intramolecular ring‐closing metathesis to access a library of novel tricyclic coumarin heterocycles and pentacyclic coumarin macrocycles having different ring systems.