We describe conjugated polymers entwined around Cu I with alternating a-quaterthienyl (poly[Cu(T 2 ) 2 ]) or 3 ',4',3'''',4''''-tetrahexyl-a-sexythienyl (poly[Cu(T 3 ) 2 ]) moieties and 1,10-phenanthroline complexing sites. Our strategy is to synthesise the 2,9-bis(oligothienyl)-1,10-phenanthroline precursors, then to assemble these ligands by means of Cu I templating followed by electropolymerisation. Poly[Cu(T 2 ) 2 ] shows separate electroactivities for Cu redox centres and conjugated backbones, whereas the electroactivities overlap in the case of poly[Cu(T 3 ) 2 ]. An X-ray absorption study on these polymers in their reduced state at the Cu-K edge identifies, in both cases, four nitrogen atoms as the closest copper(i) neighbours. For poly[Cu(T 2 ) 2 ], the Cu I environment is a distorted tetrahedron similar to a monomer model compound, but with a slightly higher number of steric constraints. The Cu I environment for poly[Cu(T 3 ) 2 ] is a less distorted tetrahedron with an unusually short Cu I ÀN average bond length. Cu I removal in poly[Cu(T 2 ) 2 ] induces an irreversible collapse of the structure, whereas the reversibility of Cu I binding is almost perfect for poly[Cu(T 3 ) 2 ], as the hexyl chains prevent irreversible gliding of the wires after copper removal. Combined electrochemical and resistance measurements reveal that the Cu centres in poly[Cu(T 2 ) 2 ] play the role of mechanical support for the structure with no significant electronic interactions with the conjugated backbone, whereas in the case of poly[Cu(T 3 ) 2 ] copper centres contribute to the conductivity of the structure.