Uniformly distributed Ag nanoparticles supported on SiO2 fiber membrane materials were successfully synthesized using electrospinning and pyrolysis. In this study, the electrostatic spinning solution is composed mainly of polyvinyl pyrrolidone, ethyl silicate (TEOS) and AgNO3. The structural and morphological studies of the materials after calcination were investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM) and thermogravimetric analysis-differential scanning calorimetry (TG-DSC). The results indicated that the samples had a rough surface structure. The load on the nanofibers was silver (Ag) metal, and the number and grain size of Ag nanoparticles increased as the relative amounts of AgNO3 increased. Furthermore, the surface enhanced Raman scattering (SERS) activity of the Ag/SiO2 was investigated using the common antibiotic enrofloxacin as a probe. It was found that the amorphous silica fiber with uniform loading of Ag nanoparticles exhibited a strong SERS enhancement effect. Due to the analytical performance, the predicted potential for SERS detection of trace antibiotics is excellent.