A simple, rapid, sensitive, and accurate method for simultaneous electrochemical determination of procaine and its metabolite (p-aminobenzoic acid, PABA) for pharmaceutical quality control and pharmacokinetic research was developed using a graphite paste electrode. The differential pulse voltammetric results revealed that procaine and p-aminobenzoic acid, respectively, showed well-defined anodic oxidation peaks on a carbon paste electrode with a current peak separation of 155 mV at a scan rate of 100 mV s −1 . This well separation of the current peaks for these two compounds in voltammetry enables us to simultaneously determine them. Good linearity (r> 0.998) between oxidation peak current and concentration was obtained in the range of 5.0×10 −7 -5.0×10 −5 M for procaine and 5.0×10 −7 -2.0×10 −5 M for PABA in pH 4.50 acetate buffer solution. The detection limit for both analytes is 5×10 −8 M (S/N=3:1). The present voltammetric method has been successfully used to determine trace p-aminobenzoic acid in procaine hydrochloride injection and procaine in plasma with a linear relationship of current to its concentration ranging from 1.0×10 −6 to 5.0×10 −5 M (correlation coefficient of 0.9981) with a low detection limit of 5.0× 10 −7 M (S/N=3:1). This validated method is promising to the study of pharmacokinetics in Sprague-Dawley rat and rabbit plasma after an intravenous administration of procaine hydrochloride injection.