Extensive magmatism in NE China, eastern Central Asian Orogenic Belt, has produced multi-stage granitic plutons and accompanying W mineralization. The Narenwula complex in the southwestern Great Xing’an Range provides important insights into the petrogenesis, geodynamic processes and relationship with W mineralization. The complex comprises granodiorites, monzogranites and granite porphyry. Mafic microgranular enclaves are common in the granodiorites, and have similar zircon U–Pb ages as their host rocks (258.5–253.9 Ma), whereas the W-bearing granitoids yield emplacement ages of 149.8–148.1 Ma. Permian granodiorites are I-type granites that are enriched in large-ion lithophile elements and light rare earth elements, and depleted in high field strength elements and heavy rare earth elements. Both the mafic microgranular enclaves and granodiorites have nearly identical zircon Hf isotopic compositions. The results suggest that the mafic microgranular enclaves and granodiorites formed by the mixing of mafic and felsic magmas. W-bearing granitoids are highly fractionated A-type granites, enriched in Rb, Th, U and Pb, and depleted in Ba, Sr, P, Ti and Eu. They have higher W concentrations and Rb/Sr ratios, and lower Nb/Ta, Zr/Hf and K/Rb ratios than the W-barren granodiorites. These data and negative ϵHf(t) values (–6.0 to –2.1) suggest that they were derived from the partial melting of ancient lower crust and subsequently underwent extreme fractional crystallization. Based on the regional geology, we propose that the granodiorites were generated in a volcanic arc setting related to the subduction of the Palaeo-Asian Ocean, whereas the W-bearing granitoids and associated deposits formed in a post-orogenic extensional setting controlled by the Mongol–Okhotsk Ocean and Palaeo-Pacific Ocean tectonic regimes.