Segmented ABA triblock and (AB)(n) multiblock copolymer systems with 6,6＇-disubstitued 2,2＇-bipyridine building blocks A and poly(oxytetramethylene) soft segments B were complexed with Cu(I) ions to obtain supramolecular polymer-ion-complexes. The complex formation resulted in a chain extension reaction in case of the ABA triblock copolymer whereas crosslinking occured in the (AB)(n)-multiblock copolymer. The resulting segmented block copolymer was a microphase separated system in bulk as concluded from transmission electron microscopy and dynamic mechanical analysis. The materials exhibited characterisric features of thermoplastic elastomers, depending on the block copolymer architecture and composition.