Supramolecularly functionalized graphene-based materials with conjugated poly(2,5-bis (3-sulfonatopropoxy)-1,4-ethynylphenylene-alt-1,4-ethynylphenylene) polyelectrolyte were successfully obtained and exhibited high conductivity and stability (even for 8 months without any aid of free polymer in solution). The excellent aqueous solubility and the possibility for self-assembly through electrostatic interactions (i.e., layer-by-layer assembly) will be realized through various applications of graphene. In addition, PPE-SO3- molecules exhibit interesting optoelectronic properties, making the resulting graphene-based materials potentially useful in is variety of optoelectronic device applications.