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Polycyclic aromatic hydrocarbons (PAHs) are of great interest due to their excellent optoelectronic properties and selfassembling properties. As a class of PAHs, star-shaped PAHs have a particular two-dimensional architecture and can self-assemble into three dimensional packed structures. Therefore, star-shaped PAHs have displayed comprehensive application in organic semiconducting materials. In this review, we will focus on the synthetic strategies toward triphenylene, trinaphthylenes, N-hetero-triphenylenes and starphenes, benzotrithiophene, truxene, and triazatruxene.