We demonstrate synthesis of diodes based on donor-acceptor bilayers consisting of fullerene (C-60) 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 similar to 3.5 nm C-60 layer on H-terminated Si and (ii) deposition of TFPP layers on C-60 layer by self-assembly process. Fourier-transform infrared spectroscopy data show that C-60 layer forms a supramolecular complex with TFPP at the interface. The current recti. cation ratio (defined as: RR = vertical bar I-1.8V/vertical bar I+1.8V) for TFPP/C-60 molecular diodes was similar to 1500. The rectification behavior has been understood using the ab initio molecular-orbital theoretical calculations. (C) 2009 Elsevier B. V. All rights reserved.