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SW Yunnan of China constituted part of the northern margin of Gondwana facing the proto-Tethys ocean in the early Paleozoic. However, the evolution of the region and its relationship with the accretionary orogenism have been poorly established. This paper reports a set of new zircon U–Pb age data and whole-rock major oxides, elemental and Sr–Nd isotopic data for early Paleozoic metavolcanic rocks from the previously defined Lancang Group and reveals the development of an Ordovician suprasubduction zone in SW Yunnan. Zircon U–Pb ages of 462 ± 6 and 454 ± 27 Ma for two representative samples indicate eruption of the volcanic rocks in the Late Ordovician. Geochemical data for the metavolcanic rocks together with other available data indicate a calc-alkaline affinity with high Al2O3 (13.04–18.77 wt%) and low TiO2 (0.64–1.00 wt%). They have Mg-numbers ranging from 62 to 50 with SiO2 of 53.57–69.10 wt%, compositionally corresponding to the high-Mg andesitic rocks. They display enrichments in LREEs and LILEs with significant Eu negative anomalies (δEu = 0.20–0.33), and depletions in HFSEs, similar to arc volcanic rocks. Their initial 87Sr/86Sr ratios range from 0.721356 to 0.722521 and εNd(t) values from −7.63 to −7.62 with Nd model ages of 2.06–2.10 Ga. Integration of ages and geochemical data with available geological observations, we propose the presence of Ordovician magmatism related to proto-Tethyan evolution in SW Yunnan and the metaigneous rocks formed in an island-arc setting. They were part of a regional accretionary orogen that extended along the northern margin of Gondwana during Neoproterozoic to early Paleozoic period. © 2015, Springer-Verlag Berlin Heidelberg.