Metamorphic and ductile deformation fabrics within the Sierra de San Luis, central Argentina, provide evidence for the Early to Middle Paleozoic development of the paleo-Pacific margin of Gondwana. Presumed Vendian-aged metasedimentary rocks within both the Sierra de San Luis and the Sierras de C¿rdoba preserve early pressure solution cleavage development. Cambrian peak metamorphism in the Sierras de C¿rdoba and Ordovician peak metamorphism in the Sierra de San Luis indicate that juxtaposition of these two terranes did not occur prior to the Late Ordovician. Peak metamorphism and regional folding of the Sierra de San Luis metasedimentary rocks is equated with early stages of the development and shortening of the Famatinian magmatic arc along the western margin of Gondwana. Extensive, NNE trending zones of upper greenschist- to amphibolite-facies ductile deformation within the Sierra de San Luis and along the western margin of the Sierra de Comechingones record the dextral oblique juxtaposition of the Sierra de San Luis terrane against the southwestern margin of the Sierras de C¿rdoba, coincident with, or closely followed by, the suture of the exotic Precordillera terrane to the western margin of Gondwana by the Early Devonian. Middle to Late Devonian restricted, lower greenschist-grade reactivation of ductile faults may record the accretion of the Chilenia terrane, the final stage of Paleozoic convergent tectonism along this segment of western Gondwana.