Time-resolved optical emission spectroscopy studies have been made to investigate the elemental/charge composition of the plasma ionic component at pulsed reflex discharge. The discharge plasma has are registered spectral lines neutral atoms and ions of the working gas Ar, Ar 1+ , Ar 2+ , and also of the cathode material: Zr, Zr 1+ , Zr 2+ , Zr 3+ . The presence of zirconium in the spectrum attests to the entry of cathode material into the plasma and its subsequent ionization. The variation of spectral line intensity with time in the early stage of the discharge and in the stage of dense plasma existence (time interval from the onset of the discharge up to 4 ms) correlates with the dynamics of plasma parameters. Characteristic times of appearance of excited atoms and ions in the plasma have been determined. The time of appearance of excited Zr * atoms is by the order of magnitude longer than that of Ar * . The stage of high-voltage mode exhibits the lines of excited Ar * , Zr * atoms and Ar +* , Zr +* ions, with the intensity of which sharply increasing during the transition to the high-current mode. The excited Ar 2+* , Zr 2+* , Zr 3+* ions appear later, when the discharge has already gone into the high-current mode.