For the last four decades, the role of polyynes such as diacetylene (HCCCCH) and triacetylene (HCCCCCCH) in the chemical evolution of the atmosphere of Saturn's moon Titan has been a subject of vigorous research. These polyacetylenes are thought to serve as an UV radiation shield in planetary environments; thus, acting as prebiotic ozone, and are considered as important constituents of the visible haze layers on Titan. However, the underlying chemical processes that initiate the formation and control the growth of polyynes have been the least understood to date. Here, we present a combined experimental, theoretical, and modeling study on the synthesis of the polyyne triacetylene (HCCCCCCH) via the bimolecular gas phase reaction of the ethynyl radical (CCH) with diacetylene (HCCCCH). This elementary reaction is rapid, has no entrance barrier, and yields the triacetylene molecule via indirect scattering dynamics through complex formation in a single collision event. Photochemical models of Titan's atmosphere imply that triacetylene may serve as a building block to synthesize even more complex polyynes such as tetraacetylene (HCCCCCCCCH).