The selection of the high-voltage supply can play an important role in the optimization of electrostatic separation processes, This paper aims to evaluate the influence of the main high-voltage parameters (waveform, polarity, level) on the efficiency of electrostatic separation, in the case of insulation-metal granular mixtures. A roll-type laboratory high-tension separator was employed for the experimental study, and the tests were carried out with samples of granular materials taken from the technological flowsheet of a recycling plant for electric wire scraps, The oscillograms of the voltage and of the current across the separator proved to be of great use for studying the transition from corona to spark discharges, The experiments, performed under various operating conditions (roll speed, roll radius, high, voltage level, interelectrode distance), show the existence of a strong interdependence between these parameters, the frequency of spark discharges, and the efficiency of the separation process, The reported results suggest that monitoring the frequency of the spark discharges could be of use for controlling the optimum operating voltage for a given electrostatic separation application, Although the full-wave rectifier allows for lower operating voltages than the half-wave rectifier, its general effectiveness in electrostatic separation processes is superior, Good insulation-metal electrostatic separation can be achieved at either positive or negative polarity of the high-voltage supply, but negative electrode energization is recommended for most industrial applications, The methodology proposed in this paper might be successfully employed for establishing the optimal operating conditions of electrode energization for other applications, such as electrostatic precipitation, plasma chemical purification of gases, or charge neutralization.