Organic semiconductor-based soft electronics has potential advantages for next-generation electronics and displays, which request mobile convenience, flexibility, light-weight, large area, etc. Organic field-effect transistors (OFET) are core elements for soft electronic applications, such as e-paper, e-book, smart card, RFID tag, photovoltaics, portable computer, sensor, memory, etc. An optimal multi-layered structure of organic semiconductor, insulator, and electrodes is required to achieve high-performance OFET. Since most organic semiconductors are self-assembled structures with weak van der Waals forces during film formation, their crystalline structures and orientation are significantly affected by environmental conditions, specifically, substrate properties of surface energy and roughness, changing the corresponding OFET. Organo-compatible insulators and surface treatments can induce the crystal structure and orientation of solution- or vacuum-processable organic semiconductors preferential to the charge-carrier transport in OFET.