A novel method for the simultaneous determination of benserazide and levodopa using capillary electrophoresis (CE)-chemiluminescence (CL) has been developed. Under the optimal conditions, the detection limits (S/N = 3) were 1.85 μg/mL for benserazide and 0.12 μg/mL for levodopa. This method was successfully applied to the determination of benserazide and levodopa in Medopar tablet, the results showed that the detected values are in accordance with those by official methods.