In this article, the effect of electrode material on the electrical breakdown, produced by a 500-ns duration high-voltage pulse in dry air at atmospheric pressure, is investigated. The configuration chosen is a pin-to-plane geometry with a gap distance of 2 mm. Both polarities of the high-voltage pulse have been investigated for three different pin electrodes. The reference pin is a copper wire of 50 mm length, while the two other pins are made of a highly resistive composite material of 240 kΩ /m, with two different lengths of 50 and 500 mm. The plane electrode is a tungsten plate of 3 cm diameter. The discharges obtained for the highly resistive wires (HRWs) can be categorized as resistive barrier discharges. Both electrical and optical characteristics of the discharges are presented and discussed. The current, voltage, and energy deposition are first analyzed. Then, the time-resolved phase-locked images of the discharges are presented, showing the propagation of the discharge filaments in the gap. The experimental results demonstrate a strong influence of the electrode material on the discharge characteristics, regardless of the polarity of the applied voltage. The main finding is that, for the same applied high-voltage pulse, the use of highly resistive materials significantly reduces the energy deposition into the discharge and the light emission from the discharge.