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A technique combining an on-capillary concentration method known as large-volume sample stacking and high-efficiency CE separation has been developed to analyze and detect three compounds in Flos Farfarae,such as rutin,quercetin and chlorogenic acid.The optimized conditions were as follows: the buffer: 40mmol/L NaH2P04 + 40 mmol/L Borax + 30% methanol (pH 8.0); the sample hydrodynamic injection of up to 4 s at 5 p.s.i..Significantly selective and sensitive improvements were observed and about 100-fold enrichment was achieved (based on peak area).This method was successfully applied to determine the three compounds in Flos Farfarae.The curve of peak response versus concentration was linear from 20 to 400μg/mL-16.5~330μg/mL and 25 to 500μg/mL.The regression coefficients were 0.9998,0.9999 and 0.9991,respectively.The detection limit of the current technique for was 0.04 μg/mL based on the signal-to-noise ratio of 3.