In ZnO the impurity ion of iron which substitutes the zinc ion must be in the Fe2+ state (d6 - configuration), but it often manifests itself as Fe3+ (d5). In 1992 the narrow line A appearing as a result of intracentral transition of Fe3+(d5) ion in the photoluminescence (PL) spectrum of ZnO at the energy of 1.7874 eV was seen for the first time. This line was accompanied by the intensive vibrational phone which was caused by the ZnO lattice phonons. In this work significant differences between the PL spectrum of ZnMnO:Fe3+ and PL spectrum of ZnO:Fe3+ are shown. In PL spectrum of ZnMnO:Fe3+ line A is splitted into two components. Under the influence of light in ZnMnO:Fe3+ the exciton localized on Mn2+ - 4O2= - cluster appears. The Auger relaxation of this exciton leads to the excitation of d5 - configuration of Fe3+ ion, not the Mn2+ ion. In our case the nonstandard Auger process with two impurity centers with 6A1 ground states takes place.