Microfluidic analytical system was developed based on annular flow of phase separation multiphase flow with a ternary water-hydrophilic/hydrophobic organic solvent solution. The analytical system was combined with on-line luminol chemiluminescence detection for catechin analysis. The water (10 mM phosphate buffer, pH 7.3)-acetonitrile-ethyl acetate mixed solution (3:8:4, volume ratio) containing 60 μM luminol and 2 mM hydrogen peroxide as a carrier was fed into the capillary tube (open-tubular fused-silica, 75 μm inner diameter, 110 cm effective length) at a flow rate of 1.0 μL·min −1 . The carrier solution showed stable chemiluminescence as a baseline on the flow chart. Eight catechins were detected as negative peaks for their antioxidant potential with different detection times. The system was applied to analyze the amounts of catechin in commercially available green tea beverages.