In this study, a deep eutectic solvent (DES)-based rapid synergistic cloud point extraction (RS-CPE) was coupled with inductively coupled plasma optical emission spectrometry (ICP-OES). This unprecedented method was used for the simultaneous determination of Cd and Ni in the medicinal plant Salvia yunnanensis C. H. Wright (S. yunnanensis). Compared with traditional CPE, RS-CPE was accomplished rapidly at room temperature. In this study, DES was used as an environmentally friendly cloud point and synergic reagent to decrease the cloud point temperature (CPT) of Triton X-114 (TX-114) and assist the subsequent rapid extraction process, thereby replacing toxic organic reagents. The experimental parameters affecting extraction efficiency were investigated and optimized. Using this combined extraction method and analytical technique, the analytical performance of ICP-OES was notably improved. Under the optimal conditions, the limits of detection (LOD) of Cd and Ni were 0.01 and 0.05 μg L-1, and the limits of quantification (LOQ) were 0.04 and 0.16 μg L-1, respectively. The enhancement factors (EFs) of Cd and Ni were 33 and 30; the spiked recoveries were 96.1–105% and 90.3–106%, respectively. The established method was applied to analyze S. yunnanensis samples with satisfactory results and provided a simple, rapid, sensitive, and green method for the determination of potentially toxic elements in medicinal herbs.