Polyaniline is one the most investigated conducting polymers owing to its unique features such as its versatile redox properties, environmental stability and reversible doping. However the low solubility in organic solvents, the poor mechanical properties and low processibility are major drawbacks for practical use and many efforts have tried to surpass these difficulties Here, we report a possibility to tune the surface and solubility properties of polyanilines using a macrocyclic compound, namely cucurbit[6]uril (CB[6]). This compound has a rigid and hydrophobic cavity and has encapsulated aniline derivatives from aqueous solution by hydrophobic, ion-dipole interactions and hydrogen bonds. We present a study highlighting the interaction between aniline monomers and CB[6] using NMR as a spectroscopic tool. In the order to better understand the structure of the inclusion complex between the two chemical species (aniline monomers and CB[6]), we have complemented these studies with molecular modeling simulations. The chemical structure of the macrocycle, CB[6], and aniline monomers is presented in the Scheme 1.schemeScheme 1: The chemical structure of CB[6] and aniline derivatives. By oxidative polymerization of host-guest complexes, polyanilines with different supramolecular structure have obtained. The polymer modifications were confirmed by spectral methods: FTIR, UV and XRD.