The interfacial electronic structure and morphology of 2,7-dioctyl[1] benzothieno[3,2b] benzothiophene (C8-BTBT) on polycrystalline Au film was investigated with photoemission spectroscopy (PES), atomic force microscopy (AFM) and grazing incidence X-ray diffraction (GIXRD). The transport barriers of holes and electrons at the interface are 1.72 eV and 2.12 eV, respectively, from the UPS measurement. There is no chemical reaction of C8-BTBT with Au from the XPS investigation of core levels Au 4f, C 1s and S 2p. The upmost molecules adopt a standing up configuration deduced from the diffraction peaks in GIXRD and the step height in AFM. Increasing order of the upright orientation of C8-BTBT molecules with film growth result in decreasing work function of the C8-BTBT thin film by forming an outward pointing dipole layer with the ordered end C-H bonds. (C) 2017 Elsevier B.V. All rights reserved.