We present the first contribution of tracing the source area of ophiolitic detritus in the Alpine molasse deposits by Raman spectroscopy. The lower Oligocene molasse deposits preserved in the Barrême basin, in the SW foreland of the western Alpine arc, are known for the sudden arrival of the first ‘exotic’ detritus coming from the internal Alpine zones. Among them, the pebbles of serpentinized peridotites have so far not been studied. We show that they only consist of antigorite serpentinite, implying that they originate from erosion of high temperature blueschists. In contrast, the upper Oligocene/lower Miocene molasse shows mixed clasts of serpentine including antigorite and lizardite without any evidence of chrysotile. This suggests that they were derived from a less metamorphosed unit such as the low temperature blueschist unit. Taking into account the sediment transport direction in the basin and the varied metamorphic characteristics of the other ocean-derived detritus, we constrain the lithologic nature of the source zones and the location of the relief zones, identified as the internal Alps, SE of the Pelvoux external crystalline massif. Available structural data and in situ thermochronological data allow the reconstruction of the Oligocene to early Miocene collisional geometry of the Palaeogene subduction wedge. This phase corresponds to two major phases of uplift evolving from a single relief zone located above the Ivrea body during early Oligocene times and persisting up to early Miocene times; then during late Oligocene/early Miocene times a second relief zone developed above the Briançonnais zone. At that time, the internal western Alps acquired its double vergency.