Practical sensing applications such as real‐time safety alerts and clinical diagnoses require sensor devices to differentiate between various target molecules with high sensitivity and selectivity, yet conventional devices such as oxide‐based chemo‐resistive sensors and metal‐based surface‐enhanced Raman spectroscopy (SERS) sensors usually do not satisfy such requirements. Here, a label‐free, chemo‐resistive/SERS multimodal sensor based on a systematically assembled 3D cross‐point multifunctional nanoarchitecture (3D‐CMA), which has unusually strong enhancements in both “chemo‐resistive” and “SERS” sensing characteristics is introduced. 3D‐CMA combines several sensing mechanisms and sensing elements via 3D integration of semiconducting SnO2 nanowire frameworks and dual‐functioning Au metallic nanoparticles. It is shown that the multimodal sensor can successfully estimate mixed‐gas compositions selectively and quantitatively at the sub‐100 ppm level, even for mixtures of gaseous aromatic compounds (nitrobenzene and toluene) with very similar molecular structures. This is enabled by combined chemo‐resistive and SERS multimodal sensing providing complementary information.