Polycrystalline diamond (PCD) exhibits a thermal conductivity similar to that of the electrically conductive chemical vapor deposition diamond (EC-CVD diamond) found to function as zero-wear electrodes at short pulse duration. In this study, PCD was used as electrodes applied to EDM on tungsten carbide. Two kinds of PCD (CTB-010 and CTH-025) with a flat surface were used. The wear of the PCD electrodes was about 1.5% for very short pulse duration such as te=1μs, but it was zero wear at te=30μs, though the wear of a Cu-W electrode was 10% even on the machine recommended conditions for the low wear. EDM experiment using a V-shaped PCD electrode with an included angle of 45° was also carried out and the performance was compared with the case using a V-shaped Cu-W electrode. Under the conditions of a no load voltage of 60V, a set peak current of 2A, and a medium pulse duration of te=15μs, there was no wear on PCD electrodes when observed under the SEM, whereas a 50μm-deep wear on the Cu-W electrodes even under the machine recommended condition for the low wear was observed.