High-Mg andesites (HMAs) are crucial for the reconstruction of plate tectonics, continental margin formation and lithospheric evolution. In this study, we present new fossil age, whole-rock geochemical and Sr–Nd isotope data on the newly discovered Dundunshan Group HMAs in the Dundunshan area of the Beishan orogen (central-southern Central Asian Orogenic Belt). The Dundunshan HMA samples are characterized by high MgO (6.47–7.02 wt%) contents and high Mg# values (67.27–68.77), with SiO2 (58.57–62.13 wt%), Al2O3 (14.49–16.07 wt%) and CaO (5.05–6.24 wt%) resembling typical HMAs. The Dundunshan HMA samples are calc-alkaline and strongly enriched in light rare earth elements (LREEs) and large-ion lithophile elements (LILEs), with slightly negative Eu anomaly and high-field-strength element (HFSE) depletions. Their (87Sr/86Sr)i ratios (0.7041–0.7057) and ϵNd(t) (3.73–5.59) indicate that the Dundunshan HMAs were mainly formed by the interactions between subducted oceanic sediment-derived melts and mantle peridotites. Fossil evidence and published radiometric age data constrain the formation of the Dundunshan HMAs to early Late Devonian time. Sedimentological features of the Middle Devonian Sangejing Formation and regional tectonic correlation suggest that the Hongliuhe–Niujuanzi–Xichangjing Ocean in the Dundunshan area was likely closed during late Middle Devonian time, and that the Dundunshan HMAs were formed in a post-collision extensional setting.