Unusual symmetry effect on the isotropization temperature of two Hexa-peri-hexabenzocoronene (HBC) derivatives is presented. Reduction of the number of substituents and maintaining a high substitution symmetry of the disk-shaped building blocks influence their thermal and self-assembly behavior. Both compounds were soluble in hot toluene and were purified by columnar chromatography and precipitation from methanol. Further characterization by verification of the purity of the compounds were done by nuclear magnetic resonance (NMR) spectroscopy, MALDI-TOF mass spectroscopy, and elemental analysis. Scanning tunneling microscopy (STM) experiments reflected the significant effect of the substitution symmetry on the self-organized monolayer between highly oriented pyrolytic graphite (HOPG) and solution by displaying novel zigzag and flower-like patterns.