Establishing a platform comprising different nanostructured oxides is an emerging idea to develop highly sensitive and selective sensing devices. Herein, novel 3D-heterostructures (p-p-n) consisting of 1D nanowires of NiO and WO 3 along with their intermediate reactive product, i.e., NiWO 4 seed, are produced by a two-steps vapor phase growth method. In-depth morphological and structural investigations describing the growth mechanism of these heterostructures are presented. Finally, the p-p-n heterostructures are integrated into conductometric sensing devices and their performances are investigated toward different gases. It is observed that by modulating the charge-carrier transport with temperature, the heterostructure sensors exhibit selective behavior toward different gas analytes. Indeed, at 300 °C, the heterostructure sensors show relatively selective behavior toward NO 2 , while at 400 °C, high selectivity toward VOCs is observed. The improvement in sensing performances is mainly based on charge carrier transport through the two interfaces (one at WO 3 /NiWO 4 (n-p) and the other at NiWO 4 /NiO (p-p)) and the modulation of charge carriers in the electron depletion layer of WO 3 and hole accumulation layer of NiO and NiWO 4 . The remarkable performance of these complex heterostructures with low ppb-level detection limits makes them excellent candidates for chemical/ gas sensing applications in e-noses.