The properties of the surface-enhanced substrate can determine the performance of the surface-enhanced Raman spectroscopy detection and have an important impact on its reliability and sensitivity. The conventional precious metal substrate produces little hot spot areas and has weak enhancement effect which has greatly limited the development of surface-enhanced Raman spectra. To address this, by introducing metal-organic framework materials MIL-53 and compounding the silver nanoparticles, combined with the physical and chemical enhancement, a highly sensitive surface-enhanced substrate was prepared in this paper. This method achieves high sensitivity of oil-dissolved furfural detection. In the experiment, the pore structure size was adjusted and the hydrogen bonding sites were controlled by changing the effective concentration of metal particles, so that the enrichment effect could be fully exerted. The detection of common aging characteristics of furfural, acetone and methanol in transformer oil through the substrate reflects the enhanced selectivity of furfural molecule detection, which can be used in detection of furfural dissolved in oil under the interference of other aging characteristics. This method enabled the limit of detection for the dissolved furfural in oil reach 3 mg/L.