The Datong pluton, the largest early Palaeozoic granitoid in the Western Kunlun Orogenic Belt (WKOB) in NW China, is a typical appinite-granite complex. It consists of diorites, quartz diorites, monzodiorites, quartz monzodiorites, monzonites, quartz monzonites, syenites, granodiorites and monzogranites. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb dating yielded crystallization ages of 459 ± 3 Ma for the quartz monzonites and 452 ± 5 Ma for the monzogranites (Late Ordovician). The rocks possess a wide range of SiO2 (56.0–73.4 wt %), MgO (0.17–4.55 wt %) and Mg no. (25–60), with high K2O (2.83–5.29 wt %) contents, exhibiting high-K calc-alkaline to shoshonitic traits. They are characterized by enrichments in large-ion lithophile elements (LILEs) and light rare Earth elements (LREEs), as well as depletions in high-field-strength elements (HFSEs). The rocks have initial 87Sr/86Sr ratios of 0.7086–0.7185, negative εNd(t) values of –3.72 to –1.79 and εHf(t) values vary from –1.6 to +4.7. These features are modelled to show that they were most likely derived from an enriched lithospheric mantle source and that fractional crystallization with minor crustal contamination was involved in their petrogenetic process. Considering the distribution and chronology of the Palaeozoic intrusions – such as Kegang, Bulong, Qiukesu, Yierba, North Kudi, Dongbake, Buya, Ayilixi and Warengzilafu granitoid plutons with ages of c. 420–530 Ma – in conjunction with the Palaeozoic metamorphic overprinting in the WKOB, we propose a divergent double-subduction model to explain the destruction of the Proto-Tethys Ocean and suggest that the Datong pluton was likely emplaced in a post-collisional setting following the termination of subduction in response to slab break-off.