Abstract: A method of HPLC combined with electrochemiluminescence detection for the determination of ascorbic acid was established on the basis of that the ascorbic acid could be oxidized by Mn(Ⅲ) which was produced under conditions of constant current electrodecomposition,resulting a chemiluminescence.The proposed method has a detection limit of 3×10-5g·L-1.RSD of 2.2% (n=11,at concentration level of 5.0×10-2g·L-1) and linearity range from 1×10-4 to 1×10-1g·L-1.Ascorbic acid in several complex samples such as beer,serum and urine was determined under optimized conditions with satisfactory results.