|A new supramolecular polymer containing urea-cytosine (UrCy) quadruple hydrogen-bonding moieties possessing a high association constant (Ka > 106 M-1) was synthesized at high yield (96%) in kilogram-scale. The synthesized telechelic macromer dissolved in solution can lead to substantial change in solution viscoelasticity and can self-assembly owing to the noncovalent nature of supramolecular polymerization. Along with the increased concentration of UrCy in the solution, the spherical assemblies gradually transformed to ordered lamellar phase with an extremely high degree of polymerization. In addition, the dynamic behavior of UrCy units causes a sudden phase transition in the bulk, revealing an interesting order-disorder transition from crystalline solid to a liquid state. This new discovered material has excellent polymer-like features far different to those can be found in the existing systems. A facile path is recommended for kilogram-scale production of this new supramolecular polymeric material.