Ultralong titanyl phthalocyanine (TiOPc) sub-micron wires have been synthesized by a novel solution-based self- assembly method. By using different solvents, changing the mass concentration and the solvent vapor pressure, the length and the shape of the wires can be adjusted. The mixed-phase properties of the TiOPc sub-micron wires were investigated by the ultraviolet-visible (UV-vis) absorption spectrum and X-ray diffraction. Organic transistors based on these wires were studied, which show the typical p-channel characteristics.