The first basement outcrops west of the Río de La Plata craton are metabasaltic and metasedimentary units of the Sierra Chica belt, part of the Eastern Sierras Pampeanas. These are orthoamphibolites and subordinate garnet-biotite gneisses and metacarbonate sequences that are intruded by Cambrian calc-alkaline and peraluminous rocks of the Pampean Orogeny. In accordance with one of the leading tectonic models for the region, new provenance data from this research suggest that the metabasaltic-metasedimentary association represents the proximal deposits of a Late Neoproterozoic island-arc. This contribution brings new geochemical and geochronological evidence from orthoamphibolites located on different sites along the Sierra Chica belt, which are interbedded with metacarbonate and gneisses outcrops, showing tholeiitic compositions, island-arc related tectonic settings, and Cryogenian to Ediacaran crystallization ages. Moreover, silicate-rich metacarbonates interbedded within the same sequences yielded a maximum depositional age of 569 Ma, reinforcing the assumed age for the sequence. All things considered, these rocks are interpreted as old basic lava flows and gabbro dikes linked to an island-arc activity, interspersed within the carbonatic and siliciclastic shelf sediments, together constituting the Neoproterozoic Córdoba Arc from the Sierra Chica belt. A depositional analogy with the present-day Caribbean island-arcs deposits suggests that these sequences could have been part of Oceanic Arc Depositional Systems (OADS) during the diachronous closure of the Goiás ocean and the final assembly of West Gondwana. Overlapping thermo-tectonic processes associated with the Pampean Orogeny are ubiquitous throughout all the studied outcrops, as evidenced by the petrography, the zircon morphology, and the U-Pb results, indicating a complex scenario towards a Late Cambrian slab break-off event.