The possibility of non-destructive elemental analysis makes PIXE a very attractive technique in archaeological provenance studies. This technique has been fruitfully implemented on two different facilities to address the issue of obsidian provenance in the Mediterranean and in surrounding regions. At C2RMF, we took advantage of the possibility to analyze large archaeological pieces with the external micro-beam set-up. At CENBG, we used the nuclear microprobe providing a 5 μm beam diameter in large scans (700 × 700 μm2) to control the homogeneity of elemental distribution. In both cases we dosed the same set of 13 elements: Na, Al, Si, K, Ca, Ti, Mn, Fe, Zn, Ga, Rb, Sr and Zr. While at C2RMF, two Si(Li) detectors were used simultaneously to measure all elements at once with 3 MeV protons, at CENBG where only one detector was available, the light elements Na to Fe were determined with a 1.5 MeV beam, and the heavy ones, including Fe, with a beam energy of 2.7 MeV. In Western Mediterranean, it is possible with PIXE to differentiate all obsidian sources of archaeological significance. Examples are given of obsidian provenances from Neolithic sites of France and from the islands of Corsica and Sardinia. In the Near East, we can differentiate the Cappadocian and Eastern Anatolian obsidian sources used during the early Neolithic. This is illustrated by examples taken from Neolithic sites of the Middle Euphrates Valley (Syria).