Fault-dismembered segments of a distinctive, extensive, highly allochthonous, and tectonically significant Ordovician (ca. 480–460 Ma) basin, which contains suites of bimodal metavolcanic rocks, associated base metal deposits, and thick immature deep-water (turbiditic) metasediments, occur in parts of the southern Appalachian Talladega belt, eastern Blue Ridge, and Inner Piedmont of Alabama, Georgia, and North and South Carolina. The basin’s predominantly metasedimentary strata display geochemical and isotopic evidence of a mixed provenance, including an adjacent active volcanic arc and a provenance of mica (clay)-rich sedimentary and felsic plutonic rocks consistent with Laurentian (Grenvillian) upper-crustal continental rocks and their passive-margin cover sequences. Geochemical characteristics of the subordinate intercalated bimodal metavolcanic rocks indicate formation in a suprasubduction environment, most likely a back-arc basin, whereas characteristics of metasedimentary units suggest deposition above Neoproterozoic rift and outer-margin lower Paleozoic slope and rise sediments within a marginal basin along Ordovician Laurentia’s Iapetus margin. This tectonic setting indicates that southernmost Appalachian Ordovician orogenesis (Taconic orogeny) began as an extensional accretionary orogen along the outer margin of Laurentia, rather than in an exotic (non-Laurentian) arc collisional setting. B-type subduction polarity requires that the associated arc-trench system formed southeast of the palinspastic position of the back-arc basin. This scenario can explain several unique features of the southern Appalachian Taconic orogen, including: the palinspastic geographic ordering of key tectonic elements (i.e., back-arc, arc, etc.), and a lack of (1) an obducted arc sensu stricto on the Laurentian margin, (2) widespread Ordovician regional metamorphism, and (3) Taconic klippen to supply detritus to the Taconic foreland basin.