A novel and simple coacervate microdroplet-based detection platform for the quantification of trace hydrophobic analytes is presented. Herein, taking advantage of the effective encapsulation and enrichment performance of the condensed coacervates, plasmonic metallic silver nanoparticles (AgNPs) and target hydrophobic analytes are simultaneously concentrated into a single microdroplet. The coencapsulation of AgNPs within coacervates promotes the formation of aggregates with a lot of "hot spots" for surface-enhanced Raman scattering (SERS) enhancement, facilitating the sensitive analysis of hydrophobic analytes by SERS technology. Such plasmonic coacervates are easily prepared and exhibit good reproducibility and signal uniformity. Optimized SERS performance by modulating the volume of encapsulated AgNPs enables quantitative determination of hydrophobic analytes of Nile Red, chlorpyrifos, benzo[e]pyrene, 20 and 50 nm polystyrene nanoplastics with low detection limits of 10-12 M, 10-9 M, 10-10 M, 0.05 ppb, and 0.5 ppb, and an approximately linear correlation between SERS signals and the analytical concentrations. This study opens a new convenient SERS platform for the ultrasensitive detection of hydrophobic hazardous substances, potentially becoming a rapid analysis method for extensive applications ranging from food safety to environment monitoring.