Direct difunctionalization of chemically distinct ortho - and peri -C-H bonds of fused hetero(arenes) is illustrated through an unusual one-pot domino {4 + 2 & 5 + 2} double annulation with alkynes for the first time. This process is viable under Ru( ii )-catalysis using a sulfoximine directing group and builds four bonds (CC)(CN) and (CC)(CO) in a single operation. Such synthetic manifestation offers access to uncommon 6,7-fused oxepino-pyridine skeletons. DFT calculations provide mechanistic insight into this double annulation of naphthoic acid derivatives with alkynes and corroborate the participation of a ruthena-oxabicyclooctene intermediate, which is responsible for the rare 7-membered ring formation. Direct difunctionalization of chemically distinct ortho - and peri -C-H bonds of fused hetero(arenes) is illustrated through an unusual one-pot domino {4 + 2 & 5 + 2} double annulation with alkynes for the first time.