A series of molecular rectangles have been synthesized by self-assembly using Re(CO)(5)OTf, 4,4'-bipyridine and an alcohol or water. The rectangles have been characterized by elemental analysis as well as IR,H-1 NMR and UV-visible spectroscopies, and in one case cyclic voltammetry and an X-ray structure determination. These complexes are representatives of a new structural class of molecular parallelograms containing the unusual combination of carbon monoxide and alkoxide ligands around a Re(I) center.