A large analytical programme involving both obsidian source characterization and obsidian artefact sourcing was initiated recently within the framework of the French archaeological mission ‘Caucasus’. The results will be presented in two parts: the first part, this paper, deals with the presentation and characterization of obsidian outcrops in the southern Caucasus, while the second presents some results obtained from a selection of artefacts originating from different Armenian sites dated to between the Upper Palaeolithic and the Late Bronze Age. The same analytical method, LA–ICP–MS (laser ablation inductively coupled plasma mass spectrometry), has been used to characterize all the studied samples (both geological and archaeological). This method is more and more widely used to determine the elemental composition of obsidian artefacts, as it causes minimal damage to the studied objects. We present in this first part new geochemical analyses on geological obsidians originating from the southern Caucasus (Armenia, Georgia) and eastern Turkey. These data enhance our knowledge of the obsidian sources in these regions. A simple methodology, based on the use of three diagrams, is proposed to easily differentiate the deposits and to study the early exploitation of this material in the southern Caucasus.