Tools capable of exploring matter with ultimate spatial resolution have attracted a tremendous interest over the past decades. Among those, scanning probe microscopes (SPMs) have played a pre-eminent role allowing one to visualize, manipulate and address electronic, magnetic or optical properties with atomic-scale resolution. A drawback of SPMs is their very low chemical sensitivity, a constant limitation for investigations aiming at characterizing fundamental chemical phenomena occurring at the molecular level. Conversely, Raman spectroscopy constitutes a powerful chemical identification tool that provides extremely detailed and direct information on the structure of organic species, but whose spatial resolution is intrinsically limited by diffraction. The concept of AtomiChem is to combine these two approaches, namely STM and Raman spectroscopy, to develop an ultimate tip-enhanced Raman spectroscopy (TERS) instrumentation, also named “Pico-Raman”, allowing one to characterize the chemical structure of organic systems with sub-nanometer resolution. The two main objectives of the proposal are: i. Developing and setting-up a pico-Raman apparatus for chemically resolved investigations at the atomic-scale, fully compatible with ultra-high vacuum (UHV) and low-temperature. A final objective of the project is to provide a “plug-and-play” efficient solution. ii. Developing an operando pico-Raman approach to probe the so-far non-reachable structure-function relationships in single-molecule devices