The Central Ailaoshan (CAL) ophiolite represents an important tectonic component of the Jinshajiang– Ailaoshan–Song Ma suture zone separating the South China and Indochina blocks in the mainland SE Asia. The CAL ophiolite occurs as a complex tectonic mélange, and preserves the history of the opening and closure of the once vast Jinshajiang–Ailaoshan–Song Ma branch of the Paleotethys. New and existing geological data indicate that the CAL ophiolite contains magmatic rocks generated by: (1) L. Devonian–E. Carboniferous (ca. 380–330 Ma) volcanic passive margin-breakup development in the NW Gondwana margin; (2) L. Permian (ca. 258 Ma) Emeishan large igneous province-related continental rift magmatism, together with (and intruded by) (3) earliest M. Triassic (ca. 244 Ma) continent–continent syn-collisional S-type granitoids. The Devono-Carboniferous suites of the CAL ophiolite are highly comparable with many continental margin-type Alpine Tethyan ophiolites. In addition, the various CAL magmatic suites have strong South China block-affinities with coeval magmatism particularly in the western South China block, Jinshajiang-, Song Ma-, and Song Da terranes.