An optically isolated electronic trigger system for a pulsed Van de Graaff electron accelerator, producing an external pretrigger pulse 75 ns before arrival of the electron pulse at the target, is described. The total time jitter between trigger signal and electron pulse is 50 ps. The measurement of optical and electrical transients on a subnanosecond time scale with a sequential sampling oscilloscope is demonstrated. The contribution of various parts of the equipment to the total jitter is discussed. Those contributions to the jitter due to the electron transit time fluctuations in the accelerator assuming a constant acceleration voltage gradient and to the shot noise in the photomultiplier detector of the trigger system are calculated to be 5 ps and 12 to 21 ps respectively. Comparison with the experimental results leads to the conclusion that a considerable part of the total jitter may be attributed to acceleration voltage gradient fluctuations, to accelerator vibrations and possibly to density fluctuations in the insulation gas. Possible improvements of the trigger system are discussed. The apparatus is used for pulse radiolysis experiments with subnanosecond time resolution down to 100 ps in combination with subnanosecond time duration electron pulses.