Polyaniline (PANi)/graphene nanocomposites have attracted tremendous interest because of their great potential in electrochemical energy storage applications, especially supercapacitors. We herein focus on the composite synthesis, device fabrication and particularly various techniques for the improvement of electrochemical performance. It is imperative to take close control of the interface in these nanostructured composites, which thus would lead to the desired synergistic effects and cyclic stability with the efficient diffusion of electrolyte ions and electrons. Challenges and perspectives are discussed for the development of highly efficient PANi/graphene electrodes for supercapacitors.