Organic synthesis based on straightforward transformations is essential for environmentally benign manufacturing for the invention of novel pharmaceuticals, agrochemicals, and organoelectronic materials in order to ultimately realize a sustainable society. Metal-catalyzed C-H bond-cleaving functionalization has become a promising method for achieving the above goal. For site-selective C-H bond cleavage, so-called directing groups, i.e., ligands attached to substrates, are employed. Commonly utilized directing groups are carbonyls, imines, carboxyls, amides, and pyridyls, which σ-donate electron pairs to metals. On the other hand, unsaturated substrates such as alkenes and alkynes, which participate largely as reactants in organic synthesis, are prepared readily by a wide variety of synthetic transformations and are also employed as reactants in organometallic chemistry. Moreover, such unsaturated groups form complexes with some metals by ligation of their p orbitals via donation and back-donation. However, the use of unsaturated bonds as directing groups has not been studied extensively. We have been involved in the development of methods for the cleavage of C-H bonds by means of transition-metal catalysts to achieve new carbon-carbon bond-forming reactions and incidentally came to focus on the alkynoxy group (-OC≡C-), which shows a ketene-like resonance structure. We expected the alkynoxy group to interact electrophilically with a low-valent transition-metal complex in order to cleave adjacent C-H bonds. In this Account, we summarize our recent achievements on C-H activation based on interactions of palladium with the alkynoxy group in alkynyl aryl ethers. The alkynoxy group plays two roles in the transformation: as a directing group for adjacent C-H bond activation and as an acceptor for the carbon and hydrogen fragments. A typical example is palladium-catalyzed ortho-C-H bond activation in alkynoxyarenes followed by sequential insertion/annulation with internal alkynes and the alkynoxy group to produce 2-methylidene-2H-1-benzopyrans. Mechanistic studies have shown that the presence of both oxygen and alkynyl moieties is essential for selective ortho-C-H bond activation and subsequent annulation. In addition to internal alkynes, norbornene, allenes, isocyanates, and ketenes produce the corresponding oxacycles. It is worthy of note that benzoxadinones formed by the reaction with isocyanates exhibit solid-state luminescence. In addition, 2-methylphenyl alkynyl ethers and 2-alkynoxybiaryls undergo intramolecular annulation at the benzylic γ-position and aryl δ-position via C-H bond activation to give benzofurans and dibenzopyrans, respectively. The disclosed methods allow us to construct useful π-conjugated systems in a straightforward manner.