Sol-gel tunable red-green-blue (RGB) emission (see figure) is achieved through the functionalization of oligo(p-phenylenevinylene)s (OPVs) with polarizable functional groups, which produce molecular and supramolecular pathways and hence the modulation of the emission properties. The molecules reported are the first example of OPV-based non-hydrogen-bonded quadrupolar pi-gels with tunable emission colors and are excellent light-harvesting scaffolds.