The epitaxial orientations of highly crystalline para-sexiphenyl (C 36H 26) films on mica (001) surfaces are investigated by selected area electron diffraction (SAED) and transmission electron microscopy (TEM). Films at the early growth stage (growth time 26 s) and at an advanced growth stage (growth time 10 min) are studied. Films at the early growth stage exhibit only three-dimensional islands with an average size of 60×30×10 nm 3, whereas films at an advanced growth stage consist of long oriented nano-fibres with a needle-like morphology. We identified three different types of epitaxial relations between the mica (001) substrate and the sexiphenyl crystallites, which are the same in both growth stages. Moreover, within a single island as well as within a single fibre crystalline domains with these three epitaxial orientations are observed. At the advanced growth stage, these domains are aligned antiparallel or perpendicular to the fibre axes; the typical size of the domains is 20 nm.