Plasmonic coupling between two or more metal nanostructures has attracted significant interest, since this fascinating near-field interaction is more effective for the aggregation/magnification of the incident light intensity compared to normal surface-plasmon-resonance (SPR) of single nanostructures. Herein, we report, for the first time, an IR-driven strong plasmonic coupling in an unusual metal/non-metal heterostructure system. This system is fabricated through random assemblage of Ag nanorices (NRs) onto W18O49 nanowires (NWs) film with F-doped SnO2 glass as substrate. Through the 3D-finite element simulation, we demonstrate that the plasmonic coupling between Ag NRs and W18O49 NWs significantly enhances the localized electric fields at the "hot spots". This achieved magnitudes of 10(1)-10(4) times of that of incident light, thus leading to the promoted generation of plasmonic "hot-electrons". Moreover, the resonance excitation of plasmonic coupling on the heterostructures not only induces ultrafast electron transfer from W18O49 to Ag hetero-components, but also the photothermal effect to increase the localized temperature. Upon SPR-coupling excitation, the Ag/W18O49 heterostructures film exhibits a remarkable enhancement of the photo/thermal catalytic activity for H-2 evolution from ammonia borane compared to that of either the Ag NRs ((similar to)8.2 x) or W18O49 NWs ((similar to)9.0 x) films. Notably, we observed an obvious H-2 evolution over the Ag/W18O49 heterostructures film under natural sunlight irradiation.