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[Display omitted] • Bimetallic MOFs-derived hierarchical WO 3 /ZnWO 4 /CoWO 4 heterostructures are gained. • Morphology and sensing behavior of the samples are tuned by the amounts of ZIFs. • Good selectivity and stability of WO 3 -based composites can be observed at 25 °C. • Abundant polyoxometalate electron acceptors are distributed on the coarse surface. • Sensing mechanism is relied on the rapid transport of carriers and plentiful POMs. Bimetallic MOFs-derived hierarchical WO 3 /ZnWO 4 /CoWO 4 heterostructures were prepared by electrospinning for achieving superior n-butanol-sensing property at low operating temperatures. Porous chain-like structures can gradually transformed into porous mulberry-like structures composed of various accumulated particles as increasing the additive amount of Zn/Co-ZIFs. High selectivity and stability of WO 3 -based composites to 100 ppm n-butanol can be observed at 25 °C, including the large sensitivity of 32 and the fast response/recovery times of 115/179 s. The enhanced gas-sensing performance is primarily ascribed to the increased specific surface area, plentiful polyoxometalate, and effective heterojunctions, obviously promoting surface/interface absorption behavior and electron transport process. [ABSTRACT FROM AUTHOR]