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In a wide variety of high-power pulsed devices, the megavolt switch plays a key role in the system performance. A capacitance-resistance coupling structure was designed to produce UV light which triggered the switch to decrease the breakdown jitter. High-speed electrical measurements with a circuit integrating probe in the nanosecond range were employed to measure the voltage before the switch. From the experimental results, the breakdown characteristic of a 3-MV UV-illumination switch was obtained in the range of 1.6-2.5 MV: The jitter of the breakdown voltage is lower than 25 kV, and the jitter of the breakdown time is shorter than 5 ns.