Capillary electrophoresis (CE) with on-line direct chemiluminescence (CL) detection was first used in detecting protocatechuic aldehyde (PAH) and protocatechuic acid (PA) in their pharmaceutical preparations. It was found that the weak CL produced from the reaction of luminol with ferricyanide in an alkaline solution was strongly increased by PAH and PA which was separated by CE. Parameters affecting separation process and CL detection have been examined in detail. Under the optimum conditions, the baseline separation of PAH and PA was obtained within 6 min. The relative standard deviation (R.S.D.) for the analysis of PAH and PA was less than 1.1% for the migration time and 1.6% for the peak height. The detection limits (S/N=3) of PAH and PA were 7.0 x 10(-8)M and 5.0 x10(-8)M, respectively. The proposed method has been satisfactorily applied to the determination of PAH and PA in Salivia miltorrhrza pharmaceutical preparations.