Systems that are capable of robustly reproducing single-molecule junctions are an essential prerequisite for enabling the wide-spread testing of molecular electronic properties, the eventual application of molecular electronic devices, and the development of single-molecule based electrical and optical diagnostics. Here, a new approach is proposed for achieving a reliable single-molecule break junction system by using a microelectromechanical system device on a chip. It is demonstrated that the platform can (i) provide subnanometer mechanical resolution over a wide temperature range (≈77-300 K), (ii) provide mechanical stability on par with scanning tunneling microscopy and mechanically controllable break junction systems, and (iii) operate in a variety of environmental conditions. Given these fundamental device performance properties, the electrical characteristics of two standard molecules (hexane-dithiol and biphenyl-dithiol) at the singlemolecule level, and their stability in the junction at both room and cryogenic temperatures (≈77 K) are studied. One of the possible distinctive applications of the system is demonstrated, i.e., observing real-time Raman scattering in a single-molecule junction. This approach may pave a way to achieving high-throughput electrical characterization of single-molecule devices and provide a reliable platform for the convenient characterization and practical application of single-molecule electronic systems in the future.