In an aqueous piperacillin sodium solution, a well-defined single wave or single peak was observed by direct current(DC) polarography or differential pulse polarography(DPP). The peak potential change per pH unit was -54 mV in the phosphate buffer at $18^{circ}C$, which indicated that protons were involved in the electrochemical reduction of the 2,3-dioxopiperazine moiety of piperacillin sodium with a $H^{+}e^{-}$ ratio of one. Using a phosphate buffer of pH 4.3, the $1.0{times}10^{-7}$ M piperacillin sodium single peak could be determined by DPP with relative standard deviation of 1.6 %(n=3). Piperacillin sodium could be analyzed with-out interference from penicillin G-potassium, which enabled the employment of DPP as a fast and simple technique for monitoring the synthetic process of the antibiotic.