Highly sensitive sub-ppb level NO2 gas sensors based on hybrid heterostructures made out of metal nanoparticles (NPs) and porous metal oxide semiconductors are of great significance in environmental monitoring and medical diagnosis. Herein, we report the successful synthesis of a Pd nanoparticle decorated porous TiO2 nanostructure-based hybrid Schottky heterostructure and its application in room temperature (RT ∼ 30 °C) low-ppb level NO2 detection under UV activation. The optimized TiO2@Pd 50 hybrid heterogeneous nanostructures (HNs) showed an excellent NO2 (100 ppm) gas sensing response of 175.42%, excellent cycling stability, outstanding selectivity, low detection limit (∼82 ppb) and fast response/recovery speed (48/72 s) under UV illumination. Moreover, the as-prepared hybrid sensor demonstrates reliable reproducibility and robust sensing responses under various elevated temperatures (30-200 °C) and relative humidity conditions (0-80% RH) towards NO2. The excellent RT NO2 gas sensing properties of TiO2@Pd 50 HNs are primarily attributed to the improved surface area, enhanced oxygen vacancies, low charge carrier recombination, and catalytic effect triggered by the hot electrons induced, from the localized plasmonic resonance effect of Pd NPs, resulting in effective NO2 adsorption/desorption dynamics. The Schottky junction formation at the hybrid TiO2@Pd 50 HNs interface effectively aids in the separation of charge carriers via band bending, leading to excellent charge transfer between the NO2 molecules and the heterointerface under UV light, yielding substantial sensitivity and selectivity to NO2. The present work is expected to provide a strategic route for designing and fabricating sub-ppb level high-performance NO2 sensors based on hybrid heterostructures.