A water-soluble supramolecular polymer with a high degree of polymerization and viscosity has been constructed based on the strong host–guest interaction between p-sulfonatocalixarenes (SC4As) and viologen. A homoditopic doubly ethyl-bridged bis(p-sulfonatocalixarene) (d-SC4A) was prepared and its binding behavior towards methyl viologen compared with the singly ethyl-bridged bis(p-sulfonatocalixarene) (s-SC4A) by NMR spectroscopy and isothermal titration calorimetry. By employing a viologen dimer (bisMV4+) as the homoditopic guest, two linear AA/BB-type supramolecular polymers, d-SC4A⊃bisMV4+ and s-SC4A⊃bisMV4+, were successfully constructed. Compared with s-SC4A⊃bisMV4+, d-SC4A⊃bisMV4+ shows much higher solubility and viscosity, and has also been characterized by viscosity, diffusion-ordered NMR spectroscopy, dynamic light scattering, and atomic force microscopy measurements. Furthermore, the polymer is responsive to electrostimulus as viologen is electroactive, which was studied by cyclic voltammetry. This study represents a proof-of-principle as the polymer can potentially be applied as a self-healing and degradable polymeric material.