Abstract Working electrodes made out of pyrolytic graphite, glassy carbon, platinum and cadmium were compared for the electrochemical generation of volatile lead species. The same electrolytic cell, using each of the different working electrodes was coupled to an atomic absorption spectrometer and the experimental conditions were optimized in each case, using a univariate approach, to produce the maximum possible amount of volatile lead species. The experiments were focused on the variation of cathode hydrogen overvoltage by the application of a constant current during analysis. Under optimum conditions the performance of the electrochemical hydride generator cell should depend on the cathode material selected due to the different hydrogen overpotential of each material. The lead absorbance signal was taken as a measure of the efficiency of volatile lead species production. Best results were obtained using the Cd cathode, due to its relatively highest hydrogen overpotential, a carrier gas (Ar) flow rate of 55mLmin−1 an electrolytic current of 0.8A and a catholyte (HCl) concentration 0.05molL−1. The analytical figures of merit of the method using the Cd electrode were evaluated and the susceptibility of the method to interferences was assessed by its application to the determination of trace amounts of lead in the presence of the most significant interferents. The calibration curve was linear between 0.5 and 15μgL−1 Pb. Detection limits and characteristic mass values were 0.21μgL−1 and 0.26μgL−1 respectively. A bovine liver standard reference material and a spiked urine sample were analyzed to check accuracy.