Herein, we report the synthesis of guest-host systems comprising naphthyl-viologen-naphthyl (Np-Vio-Np) and viologen-naphthyl-viologen (Vio-Np-Vio) guest molecules and their subsequent supramolecular polymerization in the presence of a CB[8] host in water. In addition, the guest complexation of ethyl-terminated trimeric viologen (ETV) with Np-Vio-Np and CB[8] was investigated. As a result of supramolecular interactions, 2D supramolecular organic frameworks with high internal periodicity were constructed. 1H NMR studies clearly demonstrated the formation of a host-stabilized charge-transfer complex via folding back (Np-Vio-Np and Vio-Np-Vio) in the presence of CB[8]. In the case of ETV + Np-Vio-Np + CB[8], a large polymeric network was formed as indicated by the NMR titrations. UV-vis and fluorescence studies clearly confirm the formation of an inter/intra molecular CT complex upon complexation with cucurbit[8]uril. The size obtained using the dynamic light scattering (DLS) method pinpoints the formation of larger supramolecular aggregates in the order of μm through host-guest assembly, which is further complemented by FESEM and TEM. SAXS measurements indicate the formation of a 2D supramolecular polymer/polymer aggregate with long-range order.