Organic photovoltaic devices based on supramolecular complexes of porphyrin-modified gold nanoclusters with fullerene molecules are described and their promising photoelectrochemical performance reported. The incorporation of C-60 in surface holes on the porphyrin-modified gold nanoclusters (see Figure)-caused by the addition of a short-chain alkanethiol to the porphyrin modification mixture-plays a key role.