The first full characterization of 2,2′-bitellurophene polymerization and the resulting polymer is described. The electrochemical polymerization of 2,2′-bitellurophene (7) and (E,E)-1,4-diethoxy-2,5-bis[2-(tellurophen-2-yl)ethenyl]benzene (1) produces new photoluminescent conjugated polymers. Poly{(E,E)-1,4-diethoxy-2,5-bis[2-(tellurophen-2-yl)ethenyl]benzene} exhibits photoluminescent properties that qualify for potential applications as optoelectronic materials. Poly{(E,E)-1,4-diethoxy-2,5-bis[2-(tellurophen-2-yl)ethenyl]benzene} is the first polytellurophene polymer that possess photoluminescent properties.