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[Display omitted] • In situ growth of porous WO 3 /FeWO 4 hierarchical structure is originally obtained. • The distribution of p-n heterojunctions is dependent on the content of MIL-101. • The optimal operating temperatures to n-butanol can be reduced from 220 to 25 °C. • Efficient heterojunction interfaces gain surface electronic structure modulation. • A strategy of novel room temperature n-butanol-sensing performance is presented. This study originally reports the in-situ construction of porous WO 3 /FeWO 4 ribbon-like hierarchical composites with unique and intense heterojunction interface behavior and the enhanced adsorption and carrier transport capability for effectively detecting n-butanol at room temperature. The introduction of different adding amounts of MIL-101 plays the key role of the morphological evolution of WO 3 -based microstructures with the well-distributed nanoparticles in situ growth on the surface by a facile electrospinning and subsequent calcination process. Compared with pristine WO 3 , a sharp and useful reduction of the optimal operating temperature from 220 to 25 °C can be observed as the Fe component increasing, mainly owing to the inverted p-type gas sensitive response caused by the controllable variable of FeWO 4 phase in the multiple effective WO 3 -FeWO 4 heterojunctions. The optimal WO 3 /FeWO 4 composites can display the highest response of 12.3 and a relatively short response/recovery times of 110/140 s to 100 ppm n-butanol at 25 °C, together with the superior gas selectivity, repeatability, humidity and long-term stability. Density functional theory (DFT) simulation is employed for verifying the significant adsorption interaction and charge transfer between n-butanol molecule and WO 3 /FeWO 4. Regular distribution of WO 3 -FeWO 4 heterojunction interfaces can not only determine the collaborative modulation of electronic structures, but also provide the efficient surface/interface transport mechanism for MIL-101 induced one-dimensional (1D) hierarchical ribbons. Actually, the integrated gas-sensitive components based on WO 3 /FeWO 4 composites exhibit the rapid response characteristic under room temperature condition and provide a friendly strategy of optimizing the practical detection of ppm-level n-butanol for other inorganic heterogeneous sensors. [ABSTRACT FROM AUTHOR]