ortho-Benzyne, a Kekulé-type biradical is considered to be a key intermediate in the formation of polycyclic aromatic hydrocarbons (PAH) and soot. In the present work we study the ortho-benzyne self-reactions in a hot microreactor and identify the high-temperature products by IR/UV spectroscopy and by photoion mass-selected threshold photoelectron spectroscopy (ms-TPES) in a free jet. Ms-TPES confirms formation of ortho-benzyne as generated from benzocyclobutenedione, as well as benzene, biphenylene, diacetylene, and acetylene, originating from the reaction o-C₆H₄ → HCC–CCH + C₂H₂, and CH₃. PAH molecules like naphthalene, 2-ethynylnaphthalene, fluorene, phenanthrene, and triphenylene are identified based on their IR/UV spectra. By comparison with recent computations their formation starting from o-benzyne can be readily understood and supports the importance of the biradical addition (1,4-cycloaddition followed by fragmentation) pathway to PAH molecules, recently proposed by Comandini et al.