Nanolayered carbon/silica superstructures with tunable morphologies (tubes, fibers, or spheres) and sizes (micro-sized or macroscopic) were synthesized by self-assembly of perylenedidimide-bridged silsesquioxane through an easy sol-gel process followed by carbonization. The derived nanocomposite materials show interesting electrical properties, i.e., the conductivity increases exponentially with temperature.