Flexible and transparent surface-enhanced Raman scattering (SERS) substrates have gained great attention in analysis field as they offer a fast, non-destructive, and highly sensitive platform for in-situ detection. In this work, we present a facile one-pot strategy for synthesizing gold-cored silver shell nanoparticles (Au@Ag NPs) in the polyvinyl alcohol (PVA) colloid. With no other reducing agents, PVA can serve as both reducing and stabilizing agents for forming Au@Ag NPs. Besides, PVA acts as a scaffold to maintain SERS "hot-spots" by preventing nanoparticle aggregation. By using this flexible Au@Ag NPs/PVA colloid, the analytes can be extracted from rough surfaces for SERS measurements with excellent sensitivity, repeatability and stability. The SERS activity of the Au@Ag NPs/PVA remained at 89.8% even after 120 days of storage at room temperature in sealed air atmosphere. The selective detection of thiram residues on the surface of fruits and vegetables was successfully achieved. The limits of detection for thiram residues on apple and tomato surfaces were measured to be 0.58 and 0.56 ng cm, respectively, with recovery rate ranging from 91% to 107%. This work demonstrates the immense application potential of SERS colloid platform in the fields of food safety and environmental analysis.