One hundred and sixty-two pieces of obsidian have been found at 50 archaeological localities in southern France. The distribution is concentrated in the Rhône Valley, but includes sites in Drôme, and in southwest France. The obsidian is mainly from sites of the Chassey culture (4th and 3rd millennium Neolithic), but there is one Impressed Ware site (Early Neolithic) and four Copper Age sites with obsidian. Only a small proportion of the obsidian (31 pieces) consists of waste pieces, providing little evidence for on-site working. Ten pieces of obsidian were analyzed by instrumental neutron activation analysis to determine their geological provenance. Seven pieces proved to be from the Sardinian SA source, one from Lipari, and two from Pantelleria. Chronologically there is some division between sources used: all three pieces of Liparian obsidian so far identified from southern France, in this work and by earlier researchers, belong to Early Chassey contexts, and the two Pantellerian pieces are from a Copper Age dolmen. Sardinian and Liparian obsidian probably reached France by way of northern Italy, where both types were in use in contemporary cultures. The two Pantellerian pieces are evidence of some type of contact between France and the southern Mediterranean in the Copper Age, despite earlier suggestions of a very restricted distribution for the Pantellerian source. Obsidian was probably imported to southern France with other goods since the small amounts used would not warrant a separate trading network for obsidian alone.