A novel oil-in-salt liquid-phase microextraction was developed and introduced for the extraction and concentration of the trace levels of active alkaloids in Coptis chinensis prior to being analyzed by high-performance liquid chromatography with ultraviolet detection. Also, the oil-in-salt extraction mechanism was analyzed, the enrichment factor and extraction recovery were redefined, and the proposed method was compared with other methods. In the approach, the mixed solvent of pentanol/octanol (6:4, v/v) and NaCl (20% w/v) are immobilized on the permutite surface in turn to form oil-in-salt double membranes, through which the target analytes can be molecularized though salting-out effect and be extracted by organic solvent. The main parameters affecting the approach were investigated and optimized. Under the optimized conditions, the enrichment factors of the analytes were 30-117, the linear ranges were 0.002-2 μg/mL for jatrorrhizine, coptisine, and palmatine, and 0.001-3 μg/mL for berberine (r ≥ 0.9923). The limits of detection were less than 1 ng/mL. Satisfactory recoveries (84.3%-120.3%) and precision (0.9%-7.5%) were also obtained. These results confirm that the approach is a simple and reliable sample pretreatment procedure and allows for the quantification of active alkaloids in C. chinensis at actual concentration levels.