Photoionization transitions of iron ions in ZnSxSe1–x:Fe bulk crystals (0 ≤ x ≤ 1.0) were studied at temperature of 100 K. By monitoring changes of the Fe3+ electron spin resonance signal under external illumination, we are able to determine energies of Fe3+ ⇒ Fe2+ + hVB transition in different ZnSxSe1–x host crystals. At low temperature (T < 170 K) we observe metastable population of photo‐excited Fe3+ centres. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)