A KrF discharge laser (248 nm) has been used to laser trigger, by volume preionization, a spark gap switch (38–65 kV, >10 kA, 100 ns pulse duration) filled with 20 different gas mixtures using various combinations of air, Ar, CH4, H2, He, N2 SF6, and Xe. A pulsed laser interferometer is used to probe the spark column. Characteristics studied include the internal structure of the column, the arc expansion rate, and evidence of any photoionization precursor effect. Our results show that the rate of arc expansion varies depending on the average molecular weight of the mixtures. In this experiment, pure H2 has the highest rate (≊9.5×105 cm/s) and air has one of the lowest (≊7×105 cm/s) for the same hold-off voltage. A computer model of the spark column formation is able to predict most of the structure observed in the arcs, including the effect of mixing gases with widely different molecular weights. The work suggests that, under proper circumstances, the spark gap switch performance may be improved by using gases lighter than conventional switch gases such as SF6.