This Account is focused on the self-assembly of p-phenylenevinylenes, a linear pi-system, which has been extensively studied over the years due to both fundamental and technological importance. A serendipitous observation of the gelation of an oligo( p-phenylenevinylene) (OPV) derivative in nonpolar hydrocarbon solvents that led to a new class of functional materials, namely, pi-organogels, is described. Strategies to control the size, shape, and functions of the supramolecular architectures of OPV self-assemblies are highlighted. Formation of nano- to microsized helical architectures, control on chromophore packing, self-assembly induced modulation of optical properties, and application as light-harvesting assemblies are the important features of this novel class of photonically and electronically active soft materials.