We show that thin films grown by vacuum sublimation, or formed by melted powders, of semiconductor alpha-quinquethiophene (T5) exhibit a hierarchical self-affinity organization that spans scales from tens of nanometers to hundreds of micrometers. T5 organization was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), and optical microscopy. XRD showed that vacuum-evaporated T5 films were characterized by a preferred orientation of the h00 planes parallel to the glass substrate, Melting of the films followed by rapid quenching to room temperature led to the formation of micrometer-sized, single-crystal-like structures, characterized by uniaxially aligned stripes. XRD proved that the melting-quenching process enhanced molecular ordering and increased the size of domains with the molecule's long axes tilted by about 65degrees with respect to the substrate plane and piled up side-by-side along parallel columns. AFM measurements on the melt-quenched structures showed that a hierarchical architecture was built by reiteration across multiple length scales of the same recurring motif. Because of the tendency of T5 to form highly crystalline vacuum-evaporated thin films, a field-effect hole mobility comparable to state-of-the-art FET mobility of alpha-sexithiophene films was reached, without any attempt to optimize deposition conditions.