This work is devoted to the peculiarities of optical emission spectroscopy of plasma of electric arc discharge between Cu and Cr composite electrodes manufactured of two different compositions (Cr50% and Cr35% of volume) by impact sintering or pressing sintering technologies at various temperatures, namely: 650, 750, 850, 950, 1,050, and 1,150 • C. The investigations are carried out at an arc current of 3.5 A. The comparison of radial distributions of plasma temperatures, which were determined by the Boltzmann plot technique both on the basis of Cu I and Cr I spectral lines, are performed and discussed.