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In this paper, two methods, organic solvent dispersive liquid-liquid microextraction (OS-DLLME) and ionic liquid dispersive liquid-liquid microextraction (IL-DLLME) coupled with HPLC, have been critically compared and introduced for the analysis of the eight coumarins in traditional Chinese medicine (TCM) samples. Also, the apparent oil/water and ionic liquid/water partition coefficients of the target analytes were studied. The solidification phase volume or phase ratio was determined for both methods.