Die-sinking micro-electrical discharge machining (micro-EDM) is a potential method used to fabricate intricate structures without complex electrode motion planning and compensation. However, machining efficiency and poor discharge states are still bottlenecks. This study conducted a comparative investigation into the impact of ultrasonic vibration on die-sinking micro-EDM of polycrystalline diamond (PCD) and pure titanium (TA2). By adjusting discharge parameters, this study systematically evaluated the influence of ultrasonic vibration on these two materials based on discharge waveforms, motion trajectories, effective discharge counts and groove profiles. At an open-circuit voltage of 100 V, ultrasonic vibration promotes die-sinking micro-EDM of PCD. However, when the open-circuit voltage increases to 200 V, ultrasonic vibration exhibits inhibitory effects in general. Conversely, for TA2, ultrasonic vibration shows a promoting effect at both voltages, indicating the differences of ultrasonic vibration-assisted die-sinking micro-EDM on PCD and TA2. For PCD, ultrasonic cavitation improves the discharge gap environment, accelerating the removal of discharge debris. For TA2, due to its poor thermal conductivity, ultrasonic cavitation acts to break the arc, accelerating heat transfer. These research findings provide guidance for ultrasonic vibration-assisted die-sinking micro-EDM in industrial applications.