Due to hexa-peri-hexabenzocoronene (HBC)’s perfect structural and their promising electronic and optoelectronic properties, the novel derivatives of HBC have continuously attracted interest. Hexaphenylbenene, as a necessary precursor to synthesize HBC, is affected by the substituents during dehydrocyclization. New synthetic strategy of some HPC derivatives with long-chain ester groups is described. Their structures were established by 1H nuclear magnetic resonance (1HNMR) and infrared spectrometry (IR), ultraviolet-visible spectrograph (UV-vis). The results indicate that the substituents play an important role on oxydehydrogenation of HPCs.