Reversible 2D supramolecular organic frameworks encompassing branched viologen architectures and cucurbit[8]uril (CB[8]) were constructed and investigated. UV-vis investigation clearly indicates the formation and intermolecular dimerization of monocation radicals and their encapsulation into the hydrophobic CB[8] cavity which is further complemented by EPR (electron paramagnetic resonance) spectroscopy. Particle size measurements by dynamic light scattering method showed particle sizes in the range of several µm indicating larger aggregates. Zeta potential measurements suggested the instability of these particles and their tendency to form aggregates. TEM (transmission electron microscope) analysis further revealed the formation of supramolecular polymer (monocation radical with cucurbit[8]uril) whose diameter were in the range of several µm as indicated by DLS measurements; however the oxidized form, i.e., the viologen dication with cucurbit[8]uril showed dotted spots in the range of sub nanometer level. The internal periodicities of the supramolecular polymers were analyzed by SAXs (small angle X-ray scattering) measurements. Additionally, we have demonstrated that these supramolecular organic frameworks can be depolymerized by oxidation in air and again can be polymerized (intermolecular radical dimerization) by reduction under inert atmosphere demonstrating that these systems will be of broad interest.