In the emerging area of molecular electronics, fabrication of reliable metallic contacts remains one of the most critical challenges. Nanotransfer printing (nTP) is an attractive low-cost non-destructive technique to provide contact to organic monolayers. This work introduces the use of ultrasmooth gold on polymeric substrates, fabricated by using an nTP-based method, as a novel means to form metal-molecule-silicon molecular electronic test structures. We have used self-assembly to fabricate high-quality COOH-terminated alkanethiols on ultrasmooth gold. Covalent bonding to the H-Si(111) substrate was achieved through the application of moderate pressure and temperature. Because of the critical role of molecular conformation on electrical properties, infrared spectroscopy was used to explore the influence of these two parameters (P,T) on molecular ordering. Moderate conditions effectively fabricate high-quality reproducible molecular electronic test structures preserving molecular conformation with molecules bonded to both electrodes. This work proves a useful strategy for the development of hybrid nanoelectronic devices.