The ultrafast transfer of plasmon-induced hot electrons is considered an effective kinetics process to enhance the photoconversion efficiencies of semiconductors through strong localized surface plasmon resonance (LSPR) of plasmonic nanostructures. Although this classical sensitization approach is widely used in noble-metal-semiconductor systems, it remains unclear in nonmetallic plasmonic heterostructures. Here, by combining ultrafast transient absorption spectroscopy with theoretical simulations, IR-driven transfer of plasmon-induced hot electron in a nonmetallic branched heterostructure is demonstrated, which is fabricated through solvothermal growth of plasmonic W18O49 nanowires (as branches) onto TiO2 electrospun nanofibers (as backbones). The ultrafast transfer of hot electron from the W18O49 branches to the TiO2 backbones occurs within a timeframe on the order of 200 fs with very large rate constants ranging from 3.8 x 10(12) to 5.5 x 10(12) s(-1). Upon LSPR excitation by low-energy IR photons, the W18O49/TiO2 branched heterostructure exhibits obviously enhanced catalytic H-2 generation from ammonia borane compared with that of W18O49 nanowires. Further investigations by finely controlling experimental conditions unambiguously confirm that this plasmon-enhanced catalytic activity arises from the transfer of hot electron rather than from the photothermal effect.