Self-assembly of various metallo-supra-molecular coordination polyelectrolytes (MEPEs) based on pyridine ring functionalized ditopic bis-terpyridines, 2 as well as the electrochromic property is presented. MEPEs derived from electron-donating OMe functionalized ligands exhibit rapid switching rates, good reversibility, high stability, and an optical memory. The first structure-property relationships are proposed, which are needed for the de novo design and fabrication of new materials.