TTF–TCNQ co-evaporated films were fabricated on variously surface–modified substrates and the structural investigation was carried out by scanning electron microscope and X-ray diffraction measurements. It was, indicated that the molecular orientation was controllable on a properly modified substrate by chosing an evaporation condition. Furthermore, the selective growth of the TTF–TCNQ film was achieved on the surface-modified substrate using a standard photolithographic technique.