In contrast to the widespread occurrence of mafic arc magmatism during oceanic subduction, there is a general lack of such magmatism during continental subduction. This paradigm is challenged by the discovery of Early-Middle Triassic mafic igneous rocks from the southeastern margin of the North China Block (NCB), which was subducted by the South China Block (SCB) during the Triassic. Zircon U-Pb dating for these mafic rocks yields 247 ± 2–244 ± 5 Ma for their emplacement, coeval with the initial collision between the two continental blocks. These Triassic mafic rocks generally exhibit ocean island basalt (OIB)-like trace element distribution patterns, intermediate (87Sr/86Sr)i ratios of 0.7057–0.7091, weakly negative εNd(t) values of –1.2 to –3.8, and εHf(t) values of –1.3 to –3.2. Such geochemical features indicate origination from a metasomatic mantle source with involvement of felsic melts derived from dehydration melting of the previously subducting Paleo-Tethyan oceanic crust. The syn-magmatic zircons of Triassic age show variable Hf-O isotopic compositions, indicating that the crustal component was composed of both altered basaltic oceanic crust and terrigenous sediment. High Fe/Mn and Zn/Fe ratios suggest that the mantle source would mainly consist of ultramafic pyroxenites. The melt-mobile incompatible trace elements were further fractionated relative to melt-immobile trace elements during partial melting of these pyroxenites, giving rise to basaltic melts with OIB-like geochemical signatures. The mafic magmatism may be caused by tectonic extension due to rollback of the subducting Paleo-Tethyan oceanic slab in response to the initial collision of the NCB and SCB in the Early Triassic. Therefore, the syn-subduction mafic magmatism provides new geochemical evidence for tectonic transition from oceanic subduction to continental collision in east-central China.