Two polyaniline (PANI)/polymer nano-composites exhibiting huge negative dielectric permittivity have been synthesized for the first time. These novel chemical processes open a new approach for fabrication of the negative index materials (NIMs), since most of the NIMs prepared today are obtained by a structural approach – by putting together two structured materials that exhibit separately a negative permittivity and a negative permeability. We found the negative permittivity of these nano-composites is a function of the content of the dopant (i.e., PANI) as well as of the frequency. The generation of huge negative permittivity can be rationalized by the well-dispersed PANI-DBSA nano-particles which form a pseudo-continuous conductive pathway in these nano-composites.