Polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic hydrocarbons (hetero-PAHs) have been the focus of considerable attention as promising organic semiconductor materials with potential applications in organic field-effect transistors (OFETs). High-performance OFETs depend on well-ordered molecular orientation in the crystalline thin film of the active layer. Research has so far concentrated on the synthesis of fused rings in symmetric and linear structures, as exemplified by pentacene or dinaphthothienothiophene (DNTT), with the objective of expanding the π-electron system and strengthening intermolecular interactions. However, this strategy often reduces solubility, impeding solution-based fabrication, which is a key advantage of organic materials. This study investigates asymmetric molecular structures with the aim of balancing solubility with molecular orientation. It encompasses bent-shaped acenes with thiophene and thieno[2,3-b]thiophene as key structural components, as well as extended π-conjugated molecules with asymmetric terminals based on thieno[3,2-b]thiophene. To be able to control molecular orientation in asymmetric OFET materials, we also examine how molecular structure and intermolecular interactions affect charge transport properties. Our results reveal that controlling molecular shape and fine-tuning crystal structure by exploiting weak intermolecular forces, such as London dispersion forces and intermolecular iodine–iodine interactions, are important methods of achieving high charge transport properties in the design of high-performance OFET materials.