In this paper, Au@AgNPs core-shell nanoparticles are synthesized by using nano-Au seeds template method and then loaded on the poly (styrene butadiene) (SB) fiber membrane made-by electrospinning to prepare Au@AgNPs /SB as the surface enhanced Raman scattering (SERS) flexible substrate. Ultraviolet-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectroscopy are used to characterize the morphology and spectral properties of such substrate. Using Rhodamine 6G as a Raman molecular probe, on Au@AgNPs, SERS spectra are recorded after temperature-rise process, showing good thermal tolerance of Au@AgNPs /SB substrate. Therefore, Au@AgNPs /SB substrate could be utilized to detect the target samples pretreated samples at relatively high temperatures, and is conducive to improving the detection sensitivity. Taking the SERS detection of thiram as proof of concept, the limit of detection can be as low as 3.65×10-9 mol/L by using Au@AgNPs /SB extraction of thiram in a hot solution.