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Chemiresistive electronic nose (CEN) composed of villi-like nanostructures (VLNs) of SnO₂ and WO₃, and Au-functionalized VLNs was fabricated by applying electron-beam evaporation in a glancing angle deposition mode. The VLNs-based CEN with a back-heater (212 °C) shows high responses with low detection limits of parts per billion (ppb)-levels for NO and NH₃ vapors at 80% relative humidity atmosphere. The enhanced sensitivities in a high humidity condition turn out to be attributed to the spillover effect by the Au nanoparticles and a large surface-to-volume ratio in porous VLNs. Employing Au NPs on VLNs leads to the increase of O⁻ ions via the spillover effect which impedes the adsorption of water molecules, maintaining the enhanced responses against environmental humidity. Consequently, high responses for NO and NH₃ vapors maintain even in the high humidity condition. Herein, with the principal …