Stable polyyne chains terminated with biphenyl end groups (a,u-biphenylpolyynes) were synthesized in a single step through a simple procedure by using the Cadiot-Chodkiewicz reaction conditions. The a,ubiphenylpolyynes were separated through HPLC analysis and identified by means of their electronic absorption spectra. The a,u-biphenylpolyynes were studied by FT-IR and Raman spectroscopy and the spectral interpretation was supported with DFT calculations. A peculiarly low reactivity of a,u-biphenylpolyynes with ozone was observed.