The structure and electronic structure of a system comprising molecular layers of n-alkane adsorbed on Au(1 1 1) were investigated to understand the origin of the interfacial electric dipole layer. These alkane molecules are inert and thus van der Waals (vdW) interaction is the primary adsorptive force. Although these vdW interfaces are regarded as ideal physical adsorption systems unlikely to chemically interact with the metal surface, a large interfacial electric dipole layer over 1 eV is formed. It is important to elucidate the mechanism underlying the generation of such large dipole layers to understand the electrode interface in organic semiconductor devices. Thus, this paper elucidates the details of the vdW interface, in particular between tetratetracontane (TTC) and Au(1 1 1). First, the mechanism of growth of the TTC layer up to monolayer thickness was revealed using a low-energy electron-diffraction method. Second, the interface states were newly formed, as determined using angle-resolved photoelectron spectroscopy, X-ray photoemission spectroscopy, and near-edge absorption fine-structure spectroscopy. Our findings indicate, unexpectedly, that a relatively strong inter-orbital interaction governs this vdW interface, similar to a weak chemisorption system rather than a physisorption system.