To improve the drawback of surface-enhanced Raman scattering (SERS) sensors that are sensitive to excitation angles and realize the monitoring of contaminants in complex environments, we have proposed and prepared a cascaded wire-in-cavity-in-bowl (WICIB) structure on flexible polydimethysiloxane, with feasibility for plasmonic coupling. We demonstrated that the WICIB structure can serve as a highly sensitive, homogeneous, and stable SERS substrate for conventional detection. The plasmonic coupling and distribution of the enhanced electromagnetic field were evidently proven by finite element simulations, and the strong electromagnetic field was regulated around the wire and inside the cavity, which is very beneficial for the polydirectional and in situ detection. By virtue of the triple synergistic enhancement effect and unique optical properties, we successfully achieved the in situ detection of the residual pollutant molecules, ziram and 2-naphthalenethiol, in microdroplets of apple juice and lake water. Accordingly, such a flexible SERS sensor exhibits great potential in on-site environmental monitoring.