Silver is a soft, lustrous metal with the highest electrical and thermal conductivity. Due to these properties, it has many applications as a precious material both in pure and alloy form (ornaments, jewellery, utensils, coins), but also in several technological fields, considering silver compounds (e.g. photography, electric and electronic industry). As a consequence of this, silver and its by-products are regularly exposed to different atmospheres where a wide spectrum of agents (e.g. moisture, temperature, air pollutants, UV light) may cause metal corrosion and alteration of their surface characteristics and properties. The aim of this research is to deepen the potential and applicability of micro-Raman spectroscopy as a surface-sensitive technique to investigate the initial steps of atmospheric corrosion throughout the identification of surface chemical reactions and corrosion products formed on silver substrates. In a previous study, micro-Raman analysis was carried out on pure silver powder compounds, selected among the most expected corrosion products occurring on silver substrates, in order to optimize experimental conditions and to obtain reference spectra . Subsequently highly pure silver samples were exposed for 24 h to different controlled laboratory atmospheres (synthetic air, relative humidity, SO2, H2S), particularly focusing on sulfur containing gases, and the resulting surface reactions. The experiments highlight micro-Raman spectroscopy as a highly surface-sensitive technique enabling to detect both adsorbed chemical species and crystalline corrosion products of only several monolayers of thickness. Furthermore, these investigations could show the trends of primary and secondary corrosion mechanisms and their mutual interaction occurring on silver substrates. Copyright © 2013 John Wiley & Sons, Ltd.