Within the framework of the French archaeological mission ‘Caucasus’, in a previous paper we have presented new geochemical analyses on geological obsidians from the southern Caucasus (Armenia, Georgia) and eastern Turkey. We present here the second part of this research, which deals with provenance studies of archaeological obsidians from Armenia. These new data enhance our knowledge of obsidian exploitation over a period of more than 14 000 years, from the Upper Palaeolithic to the Late Bronze Age. The proposed methodology shows that source attribution can be easily made by plotting element contents and element ratios on three simple binary diagrams. The same diagrams were used for source discrimination. As the southern Caucasus is a mountainous region for which the factor of distance as the crow flies cannot be applied, we have explored the capacity of the Geographic Information System to evaluate the nature and patterns of travel costs between the sources of obsidian and the archaeological sites. The role of the secondary obsidian deposits, which enabled the populations to acquire raw material at a considerable distance from the outcrops, is also considered.