In summary, we have synthesized and isolated PF[n]CPPs (n = 10, 12, 14), which represent highly strained perfluorocarbon molecules. The synthesis of these PFCPPs was accomplished in a one-pot fashion via deprotonation of octafluorobiphenyl, transmetallation to Ni(dnbpy)Br2, and oxidant-promoted reductive elimination. The high solubility of intermediates enhanced by the n-nonyl groups of dnbpy might be the key to the success of this concise synthesis. PF[n]CPPs (n = 10, 12, and 14) were identified by spectroscopic analysis ( 19 F NMR and LDI-TOF MS), and the solid-state structures of PF [10]CPP and PF [12]CPP were unambiguously determined by X-ray crystallography. In the crystal structure, PF [10]CPP and PF [12]CPP exhibit a tubular shape, and the ring cavities are connected one-dimensionally. The dihedral angles between pairs of benzene rings in the PFCPPs are larger than those of the corresponding CPPs due to the steric repulsion between fluorine atoms. Optical and electrochemical measurements revealed wide HOMO-LUMO gaps and high electron affinity for PF[n]CPPs (n = 10 and 12), which also show strong phosphorescence at extremely low temperature. The large dihedral angles between pairs of benzene rings are presumably the reason why intersystem crossing takes place quickly in the case of PF[n]CPPs (n = 10 and 12). As this is the first efficient synthetic route to highly strained perfluoroarenes, this noble metal-free one-pot synthesis of PFCPPs represents a huge breakthrough in fluorocarbon chemistry. Apart from the obvious interesting electronic features of strained PFCPPs, it should also be possible to create highly strained molecular nanocarbon materials by further converting the reactive C-F bonds of PFCPPs. PFCPPs are not only attractive as electron-deficient aromatic materials but are also potentially applicable to further transformations for the creation of highly strained and topologically unique molecular nanocarbon materials .