A new method for the determination of baicalin with HPLC-CL was developed. The method was based on the chemiluminescence reaction between KMnO4 and baicalin sensitized from HCHO. The linear range was 3.7×10-6~9.8×10-5 mol/L with detection limit of 1.7×10-6 mol/L and the relative standard deviation was 2.5 % (Cs=6.6×10-5 mol/L, n=5). The method has been applied to the determination of baicalin in oral administration, injection, Scutellariae radix and granules with good results.