Plasmonic gold nanorods play important roles in nowadays state-of-the-art plasmonic sensing techniques. Most of the previous studies and applications focused on gold nanorods with relatively small aspect ratios, where the plasmon wavelengths are smaller than 900 nm. Gold nanorods with large aspect ratios are predicted to exhibit high refractive-index sensitivity (Langmir 2008, 24, 5233–5237.), which therefore should be promising for developing of high-performance plasmonic chemical- and bio-sensors. In this study, we developed gold nanorods with aspect ratios over 7.9, which exhibit plasmon resonances around 1064 nm. The refractive index (RI) sensitivity of these nanorods have been evaluated by varying their dielectric environment, whereby a sensitivity as high as 473 nm/RIU can be obtained. Furthermore, we have demonstrated the large-aspect-ratio nanorods as efficient substrate for surface enhanced Raman spectroscopy (SERS), where an enhancement factor (EF) as high as 9.47×10⁸ was measured using 4-methylbenzenethiol (4-MBT) as probe molecule. Finally, a type of flexible SERS substrate is developed by conjugating the gold nanorods with the polystyrene (PS) polymer. The results obtained in our study can benefit the development of plasmonic sensing techniques utilized in the near-infrared spectral region.