Increasing the sensitivity of non-noble metal surface-enhanced Raman spectroscopy (SERS) is an urgent issue that needs to be solved at present. Herein, metallic W18O49 nanowires with a strong localized surface plasmon resonance (LSPR) effect are prepared. Interestingly, the LSPR peaks of these nanowires would undergo a strong blue shift from near-infrared (NIR) to visible light regions as the aggregation degree of the nanowires increases. By narrowing the gap between the LSPR absorption peak and the Raman excitation wavelength (532 nm), the oriented W18O49 bundles with a LSPR peak centered at 561 nm have greatly improved SERS sensitivity compared with that of the dispersed nanowires with a LSPR peak centered at 1025 nm. Enhancement mechanism investigation shows that the high sensitivity can be attributed to the synergistic effect of LSPR coupling among the oriented ultrathin nanowires and oxygen vacancy (Vo)-assisted charge transfer.