The design, synthesis, and characterization of new organic semiconductors (OSCs) are important aspects for the development of next-generation optoelectronic devices. Structurally, organic semiconductors based on π-conjugated molecules can be easily modified via rational synthesis to tune multi-level self-assembled structures and discover novel chemical, optical, and electronic properties. Heteroarenes, which contain chalcogens and nitrogens in fused aromatic rings, are being developed as promising semiconducting materials for applications in a variety of electronic devices due to their outstanding optoelectronic properties. We highlight recent approaches toward realizing high performance p-channel field effect transistors based on linear heteroacenes and heteroatom annulated polycyclic aromatics (PAHs) as key functional components. These comprehensive, but carefully orchestrated approaches simultaneously address (i) practical synthesis, (ii) tunable self-assembled packing arrangement as well as (iii) high electronic performance.