The charge state and velocity of ions extracted from the expanding plasma of 5 μs vacuum arc were measured using a Time of Flight mass spectrometer. The arc was sustained between the cylindrical copper cathode of 1 mm diameter and Kovar cylindrical anode. The distance between the two electrodes is 0.1 mm. The ion charge state and velocity were detected after the arc pulse at different times (in range 20–45 μs) by opening an electronic shutter. The arc current was 35 A. It was obtained that the ion velocities are decreasing with detection times from 3.75 to 1.75 cm/μs. The fastest ions are made of a large fraction of Cu+3 with some Cu+2 while the slowest ions are made of a larger fraction of Cu+2 with some Cu+.