Two novel fac-Re(CO)(3)-based rectangles {[(CO)(3)Re-(mu-Cl)(2)Re-(CO)(3)](2 )(mu-L)(2)} (1) and {[(CO)(3)Re(mu-OC4H9)(2)Re-(CO)(3)](2) (mu-L)(2)} (2) based on new photochromic dithienylethene-containing ligand 2,7-di(pyridin-4-yl)-9,10-bis(5-chloro-2-methylthien-3-yl)-phenanthrene (L) were prepared. They displayed varying photochromic properties both in solution and in the single-crystal state. Through a judicious choice of the bridging ligands along the 3 short sides of the rectangles, the photophysical and electrochemical properties of the complexes could also be readily tuned.