Atom transfer radical polymerization (ATRP) was used in combination with Glaser type coupling, allowing the clean and efficient formation of symmetrically coupled polymers with a central diacetylene unit. The feasibility of the clean acetylene coupling was investigated with alkyne terminated poly(ethylene glycol) and poly(styrene) obtained by ATRP. The latter allowed subsequent ATRP to be carried out from the coupled products, offering opportunities for the formation of well defined functional materials with central diacetylene units. Glaser coupling was also observed as a side reaction in Huisgens-type "click" reactions of polymeric alkynes with hindered surface azide groups. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3795-3802, 2009