Graphene oxide (GO)-anisotropic noble metal hybrid systems were developed as highly sensitive and reproducible surface enhanced Raman scattering (SERS) platform, in which ultrathin GO was embedded between two metallic layers of flower-like Ag nanoparticles (AgNFs) and gold nanostars (AuNSts). Due to multi-dimensional plasmonic coupling effect, the well-designed AgNFs-GO-AuNSts sandwich structures possessed ultrahigh sensitivity with the detection limit of R6G as low as 1.0?×?10^?13 M and high enhancement factor of 2.59?×?10⁷. Additionally, the GO interlayer could function as protective shell to suppress the oxidation of bottom silver layer and efficiently position the target analytes within hot spots. These features endow the substrate with high stability and excellent reproducibility (Signal variations < 7%). Particularly, the GO sandwiched substrate can be explored for the direct capture and sensitive detection of polychlorinated biphenyls (PCBs) without any organic modifier as molecule harvester. This minimum detected concentration was estimated as low as 3.4?×?10^-6 M. The detection method based on GO mediated sandwich substrate avoids complicated surface modification manipulations and improves the substrate cleanness. Moreover, the resultant sandwich substrates can be used to recognize fingerprint peaks of different PCBs in their complex mixture, revealing great potential applications in SERS-based simultaneous detection of multiple pollutants with low affinity.