Large-scale hexagonally close-packed arrays of Au-nanobowls (Au-NBs) with tens of Ag-nanoparticles (Ag-NPs) dispersed in each bowl (denoted as Ag-NPs@Au-NB arrays) are achieved and utilized as effective surface-enhanced Raman scattering (SERS) substrates. The field enhancement benefiting from the special particle-in-cavity geometrical structure as well as the high density of SERS hot spots located in the sub-10 nm gaps between adjacent Ag-NPs and at the particle-cavity junctions all together contribute to the high SERS activity of the Ag-NPs@Au-NB arrays; meanwhile the ordered morphological features of the Ag-NPs@Au-NB arrays guarantee uniformity and reproducibility of the SERS signals. By modifying the Ag-NPs@Au-NB arrays with mono-6-thio-β-cyclodextrin, the SERS detection sensitivity to 3,3('),4,4(')-tetrachlorobiphenyl (PCB-77, one congener of polychlorinated biphenyls (PCBs, kinds of persistent organic pollutants which represent a global environmental hazard)) can be further improved and a low concentration down to 5 × 10(-7) M can still be examined, showing promising potential for application in rapid detection of trace-level PCBs in the environment.