Oligo- and poly(phenylenevinylene) (OPV, PPV) derivatives have been attracted as promising functional pi-conjugated materials for a long period. However, these compounds are structurally flexible, resulting in insufficient conjugation and instability. To address these issues, we have designed carbon-bridged oligo(phenylenevinylene)s (COPVs) having fully fused π-electron framework comprising of phenylenevinylene units which are tethered with diarylmethylenes. We have synthesized a series of COPV possessing one to six phenylenevinylene repeating unit (COPV1 - COPV6) using our recently developed reductive cyclization reaction (J. Am. Chem. Soc. 134, 19254 (2012).). Thus obtained COPVs show unique photophysical properties, such as intense absorption and emission with the fluorescence quantum yields of unity in solution irrespective of the molecular lengths. They were found to be highly stable under light irradiation and redox conditions as well. COPV derivatives were also found to be useful for optoelectronic applications. For example, quinoidal derivatives of COPVs showed very high stability and open-shell character with near infrared (NIR) absorption and emission (J. Am. Chem. Soc. 133, 16342 (2011).). A donor-acceptor connected COPV derivatives were useful as organic sensitizers in dye-sensitized solar cells (DSSCs), and achieved the power conversion efficiencies of up to 7.54% due to their structural and electronic features (Chem. Commun. 49, 582 (2013).). We also found COPVs serve as efficient molecular wire (Nat. Chem. 6, 899 (2014).) in photoinduced electron transfer systems because of its efficient conjugation effect. Participation of electron-vibration coupling is also suggested in the back electron transfer process, which makes the COPV unique among the organic single molecular wire.