Detailed measurements of ion energy distributions (IEDs) originating at different stages of a pulsed vacuum arc are studied. It is shown that for a variety of cathode materials (Al, Mg, Ti and Zr), the directed energies per charge unit of ion originating at the initial stage of the arc, i.e. in 25 µs after ignition, are close to each other and are, approximately, as much as Edir/Z ≈ 70 eV. A non-Maxwellian shape of these IEDs that is due to the presence of significant ‘tails’ of ions accelerated up to energies of a few hundred eletronvolts is found. In 100 µs after the arc ignition the directed energies relax to values that are close, principally, to values that have been measured earlier elsewhere. It is found that the ‘anomalously’ accelerated ions propagate within a narrow angle that is as much as, approximately, ±15° in relation to the plasma flux axis. These characteristics suggest that beyond the commonly adopted gas-dynamic mechanism of ion acceleration in cathode micro-jets, at the initial stage of a pulsed arc the mechanism of additional ion acceleration is presented, which is due, obviously, to a self-consistent electric field arising in front of the plasma macro-jet.