Molecular assembling is one of the current interests in the field of bottom-up nanotechnology. Self-assembled monolayers of sulfur-containing molecules or supramolecular assemblies via surface sol-gel processes formed on conductive supports are chemically robust and can be easily fabricated without sophisticated instruments. We have fabricated various types of molecular assemblies consisting of donor-acceptor pairs on the surfaces of gold and indium-tin-oxide electrodes. Build-up of three-dimensional multistructures consisting of thiol dyes and gold nanoparticles also has been successful. These assemblies showed clear photocurrent responses in photoelectro-chemical cells. In this article, we will describe recent progress on photoelectric conversion using molecular assemblies especially focused on our research results.