The anionic homopolymerization of 2,5-dimethylhexa-1.5-dien-3-yne (DMDEY) was investigated by utilizing butyllithium, sec-butyllithium diphenylmethylsodium, and naphthalene/sodium as initiators. Soluble polymers with molecular weights up to 50000 g/mol corresponding to (M) over bar(w)(M) over bar(n) of 1.05 were obtained through homopolymerization with diphenylmethylsodium as initiator in THF at low temperatures. The homopolymers consist of 1,2-linked monomer units with pendant 3-methylbut-3-en-1-yne groups.