Surface acoustic wave (SAW) devices have been widely explored for real-time monitoring of toxic and irritant chemical gases such as nitrogen oxide (NO2), but they often have issues such as a complicated process of the sensing layer, low sensitivity, long response time, irreversibility, and/or requirement of high temperatures to enhance sensitivity. Herein, we report a sensing material design for room-temperature NO2 detection based on a 3D porous architecture of Ag-decorated reduced graphene oxide-polypyrrole hybrid aerogels (rGO-PPy/Ag) and apply UV activation as an effective strategy to further enhance the NO2 sensing performance. The rGO-PPy/Ag-based SAW sensor with the UV activation exhibits high sensitivity (127.68 Hz/ppm), fast response/recovery time (36.7 s/58.5 s), excellent reproducibility and selectivity, and fast recoverability. Its enhancement mechanisms for highly sensitive and selective detection of NO2 are based on a 3D porous architecture, Ag-decorated rGO-PPy, p-p heterojunction in rGO-PPy/Ag, and UV photogenerated carriers generated in the sensing layer. The scientific findings of this work will provide the guidance for future exploration of next-generation acoustic-wave-based gas sensors.