Styryl‐ and α‐methylstyryldiphenylbismuth (I and II, respectively), and styryl and α‐methylstyryltriphenyllead and the two corresponding tin‐containing monomers (III, IV, V and VI, respectively) were synthesized. Compounds III through VI were obtained pure, but I and II contain substantial quantities of Ph3Bi and di‐ and tri‐vinyl derivatives. Homopolymers of I, III and V, as well as copolymers with methyl acrylate were synthesized radically. Monomers III, V, and VI yielded narrow MWD polymers with anionic initiators such as the potassium salt of the α‐methylstyrene dimer carbanion in THF at −80°C, while I gave a broad, bimodal MWD. Monomers II and IV did not polymerize under these conditions due to side reactions with the initiator. Glass transition temperatures, thermal stabilities and radiopacities of a number of the polymers were determined.