A discrete rhomboidal metallacycle R functionalized with bis-[2]pseudorotaxane of [Cu(phenanthroline)₂]⁺ derivatives was successfully synthesized via coordination-driven self-assembly. Furthermore, the host–guest complexation of such a bis-[2]pseudorotaxane metallacycle with a bis-pillar[5]arene (bisP5) allowed for the formation of a new family of cross-linked supramolecular polymers R⊃(bisP5)₂, which displayed interesting redox-responsive properties. By taking advantage of the substantial structural differences between the coordination geometries of [Cu(phenanthroline)₂]⁺ and [Cu(phenanthroline)₂]²⁺, the weight-average diffusion coefficients D of the supramolecular polymer were adjusted through changing the redox state of the Cu(I)/Cu(II) complexes.