A series of main chain organometallic polymers (MCOPs) containing Re(CO)(3)Cl(diimine) cores were synthesized. Three different types of polymerization reactions, including Yamamoto coupling, Heck coupling, and a new metal-mediated Schiff base formation/condensation reaction, allowed for the formation of metal polymers with 100% metal complex incorporation and average molecular weights (Ms) ranging from 25 to 850 kDa. Absorption spectroscopy, electrochemistry, and microscopy studies revealed that the type of polymerization effectively governs the physical and chemical properties of the target polymers. The electronic structures of monomeric and dimeric building units of these polymers backbones were probed by DFT and TDDFT computational methods. DFT calculations and electrochemical studies indicate that in all polymers the oxidation and reduction processes take place on Re(I) metal centers and polymer backbones, respectively. Incorporation of metal as an electron donor (D) and organic conjugated backbone as an electron acceptor (A) provides the D-A architecture.