The synthesis of the first bismuth-containing macro- molecules that exhibit phosphorescence in the solid state and in the presence of oxygen is reported. These red emissive high molecular weight polymers (> 300 kDa) feature benzobis- moles appended to a hydrocarbon scaffold, and were built via an efficient ring-opening metathesis (ROMP) protocol. More- over, our general procedure readily allows for the formation of cross-linked networks and block copolymers. Attaining stable red phosphorescence with non-toxic elements remains a chal- lenge and, thus, our new class of soluble (processable) polymeric phosphor is of great interest. Furthermore, the formation of bismuth-rich cores within organic–inorganic block copolymer spherical micelles is possible, leading to patterned arrays of bismuth in the film state.