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The Sukhothai Terrane in northern Thailand consists of continental basement and a Permo-Triassic magmatic arc related to the subduction of the main Palaeo-Tethys Ocean. The Donchai Group represents the oldest sedimentary sequence of the Sukhothai Terrane and consists mainly of meta-sandstone, quartzo-feldspathic schist, phyllite and silty slate. We present new detrital zircon U–Pb geochronology, Lu–Hf isotope data and geochemical data for the sedimentary rocks of the Donchai Group to elucidate the depositional age, provenance and nature of the group. The youngest detrital zircon ages (433–403 Ma) suggest that the Donchai Group accumulated between 433 and 368 Ma, revealing Silurian–Devonian arc magmatic rocks on the western margin of the Sukhothai Terrane. Sediments of the Donchai Group were sourced from both the continental basement and a Silurian–Early Devonian magmatic arc, suggesting a depositional setting on the continental slope of a back-arc basin along the western flank of the Sukhothai Terrane. The Silurian–Devonian arc belt in SW China probably extends to the Chiang Rai region to the west of the Sukhothai Terrane, northern Thailand, revealing the northwards subduction of the Proto-Tethys Ocean along the western Simao and Sukhothai margin during the mid-Paleozoic. The inferred arc and back-arc configuration of the Proto-Tethys Ocean in northern Thailand is comparable with that recently established in Yunnan, SW China. Supplementary material: Detrital zircon U–Pb ages and trace element analyses, zircon in-situ Lu–Hf isotopic compositions and whole-rock geochemical data are available at https://doi.org/10.6084/m9.figshare.c.6858373 [ABSTRACT FROM AUTHOR]