Abstract: We demonstrate synthesis of diodes based on donor–acceptor bilayers consisting of fullerene (C60) and tetraphenyl porphyrin derivative, that is, 5,10,15,20 tera(3-fluorophenyl)-porphyrin (TFPP), grafted on Si. These bilayer diodes were synthesized in two steps: (i) electrografting of a ∼3.5nm C60 layer on H-terminated Si and (ii) deposition of TFPP layers on C60 layer by self-assembly process. Fourier-transform infrared spectroscopy data show that C60 layer forms a supramolecular complex with TFPP at the interface. The current rectification ratio (defined as: RR=|I −1.8V/|I +1.8V) for TFPP/C60 molecular diodes was ∼1500. The rectification behavior has been understood using the ab initio molecular-orbital theoretical calculations. [Copyright &y& Elsevier]