Abstract: Phenanthrene and its derivatives are widely used in resins, dyes, agrochemicals and phytohormones. Several phenanthrene derivatives bearing alkynyl substituents were synthesized from benzyne and diynes with yields of 76%-83% in the absence of any catalyst. The structures of these compounds were characterized with 1H NMR, 13C NMR and high resolution mass spectroscopy. The results showed that the phenanthrene derivatives were formed through the intermolecular ［2+2+2］ cycloaddition reaction of two benzyne molecules and one diyne molecule, leaving one triple bond which could be further functionalized to synthesize other phenanthrene derivatives.