Molecular level alignment of components and optimum morphology of hybrid materials are of great interest in many applications. Morphology control has been extensively used as a direct tool in the evaluation of interactions and assemblies of components in thin films. It is believed that preparation method and composition are powerful tools to direct the morphology, particularly in self-assembled systems such as fullerene-based hybrid materials. The present report outlines a synergistic self-assembly of fullerenes (C(60)) and functionalized poly (p-phenylene) (PPP) to develop nanofibers with high aspect ratios. Nanostructured PPP-C(60) hybrids were prepared by direct casting of the dilute solution on solid substrates and on water under ambient conditions. The formation of whiskers with high aspect ratio and investigation of interesting photophysical properties are discussed. An amphiphilic PPP was used as a template for preparing nanohybrids of C(60) at ambient temperature and conditions.