A series of planar pi-extended Te-containing heteroacenes, termed tellura(benzo)bithiophenes, were synthesized. This new structural class of heterocycle features a tellurophene ring fused to a benzobithiophene unit with aromatic side groups (either -(C6H4Pr)-Pr-i or -C6H4OCH3) positioned at the 2- and 5-positions of the tellurophene moiety. Although attempts to enhance molecular rigidity and extend ring-framework pi-delocalization in a cumenyl (-(C6H4Pr)-Pr-i)-capped tellura(benzo)-bithiophene led to oxidation (and Te-C bond scission) to form a diene-one, the formation of an oligomeric tellura(benzo)bithiophene was possible via Kumada catalyst-transfer polycon-densation (KCTP). Furthermore, one tellura(benzo)bithiophene derivative exhibits orange-red phosphorescence at room temperature in air when incorporated into a poly(methyl methacrylate host; accompanying TD-DFT computations provided insight into a potential mechanism for the observed phosphorescence.