Alkaline basalts with geochemical features similar to those of intraplate ocean islands have been emplaced along the main trace of the Tepic-Zacoalco rift (TZR), a unique tectonic structure of the western Trans-Mexican Volcanic Belt in which extension is superimposed to a convergent margin. New geochemical and petrologic data on mafic volcanic rocks along the rift indicate the existence of a highly heterogeneous pre-subduction mantle wedge that has been slightly overprinted by slab-derived chemical agents. Most mafic volcanic rocks display geochemical and isotopic compositions that are indistinguishable from those of the Pacific islands Socorro and Isabel, and confirm the existence of an ancient, recycled, high-μ component (HIMU; μ = 238U/204Pb) in their mantle source. Olivines separated from samples carrying the HIMU signature have NiO and CaO contents similar to olivines from mid-ocean ridge basalt (MORB), indicating that the source of enrichment must be entirely hosted in peridotite. In contrast, more evolved rocks within the TZR have stronger subduction signatures and water contents, and display a distinctive isotopic array that points to slab-derived contributions. Olivines from these rocks are slightly less forsteritic but also extend to higher NiO and lower CaO contents than those from more mafic magmas, suggesting provenance from a secondary pyroxenite source. The overall geochemical evidence thus indicates that the pre-subduction background mantle wedge in western Mexico must be identical, and just as diverse, as that below the Pacific basin. Extension-driven mantle upwelling in a continental setting can only melt a dry peridotitic mantle to its lowest extents, and therefore preferentially sample its most enriched and easily fusible components. Yet the addition of even a small amount of slab-derived silica promotes a secondary petrologic transformation to pyroxene-rich lithologies that upon melting create magmas with compositions that are more akin to a volcanic arc setting.