Optical and EPR characterization of Cr and Fe doped ZnSe crystals annealed in Zn vapor revealed a strong bleaching of the divalent state of transition metal ions. Photo induced EPR kinetics were studied in 20-80K temperature range. Analysis of time-dependent data reveals Cr1+ signal rise time decreases with increasing temperature. The non-exponential decay of Cr1+ concentration were analyzed using Auger-type recombination process. The photoluminescence quantum yield of Cr2+ ions at 5E(D)→ 5T2(D) mid-IR transition excited via chromium ionization process was measured to be close to 100%. © 2014 Elsevier B.V.