We report a facile single-step one-pot solvothermal process for tailoring the Au-Ag-S microstructures as bifunctional substrates for both surface-enhanced Raman scattering (SERS) detection and photocatalytic degradation of plasticizers diethylhexyl phthalate (DEHP) and diethylhexyl adipate (DEHA). Typically, two different microstructures, the Ag2S particles inlaid Au microflowers (Ag2S-Au MFs) and Au particles decorated AgAuS microsheets (Au-AgAuS MSs) were obtained. The Ag2S-Au MF substrates finally turned out to provide 0.9 × 10(-9) and 0.9 × 10(-7) M of the limits of detection (LODs) for DEHP and DEHA in orange juice. And on the other hand, the Au-AgAuS MSs achieved complete degradation of DEHP and DEHA (1 × 10(-5) M) after 20 and 25 min of UV light irradiation, respectively. It is believed that the facile preparation and appreciable SERS and catalytic activities of these Au-Ag-S microstructures would make much sense to develop novel multifunctional sensing and monitoring devices.