Well-defined single-crystalline nanobelts with strong fluorescence were fabricated from a perylene tetracarboxylic diimide molecule modified with specific side-chains that afford flip-flap stacking, rather than the common translated stacking, between the molecules along the long axis or the nanobelt. The nanobelts thus fabricated possess highly polarized, self-waveguided emission. making them ideal candidates for application in nanolasers and other angle-dependent optical nanodevices.