Electrospinning is an attractive way to prepare nano- and macrofibers. It was demonstrated by our group that trisamides can be melt electrospun into supramolecular fibers. To establish structure property relationships regarding spinnability and morphology, melt electrospinning experiments were conducted using several classes of compounds. The number of hydrogen bonds was systematically decreased from three for trisamides, to two for bisamide and sorbitols, and to zero for perylene bisimides and tertiary trisamides. As a result, trisamides are readily spun into fibers, whereas for bisamides and sorbitols mainly electrospraying into spheres is observed. Perylene bisimides form well-defined fibers due to strong pi-pi interactions. This supramolecular fiber is interesting for many scientific disciplines.