A cruciform-shaped oligo(phenylenevinylene) (OPV) with a phosphorescent rhenium(I) chromophore incorporated at the centre and grafted triphenylamines around the periphery was designed as a new organic photovoltaic material, in which the chelation of rhenium(I) to the cruciform successfully constructs a three-dimensional intramolecular charge transfer system and extends the exciton lifetime; as a result, the rhenium-OPV complex shows a power conversion efficiency almost two times that of the metal ion-free parent compound.