We have synthesized a new homoconjugated donor-acceptor (D A) system featuring a rigid planar carbon-bridged oligo(p-phenylenevinylene) that shows efficient intramolecular charge separation (CS, 98%). The charge recombination rate is 100-times slower than that of CS, and located in the Marcus inverted region. The electronic coupling was estimated to be 1.0 x 10(3)cm(-1), which is one of the largest values among reported D A interactions.